Crystal packing and theoretical analysis of halogen- and hydrogen-bonded hydrazones from pharmaceuticals. Evidence of type I and II halogen bonds in extended chains of di­chloro­methane

The supramolecular assembly of halogenated and hydroxyl hydrazones derived from two well known pharmaceuticals, isoniazid (IsX, where X = I, Br, OH) and hydralazine (HyX, where X = I, Br, OH), was studied by X-ray crystallography and theoretical methods. Crystal packing of IsI and HyI shows weak I...N and I...π halogen bonds, whereas the hydrogen bonds are dominant in the brominated scaffolds IsBr and HyBr. Although the calculated I...N interaction strength appears almost three times weaker than the O—H...N contacts in the isoniazid-based hydrazones, the higher directionality of the halogen bonds induces a linear and planar architecture of self-complementary tectons, observed only with the help of a bridging water molecule in the case of IsOH. Finally, the X-ray structure of HyOH is characterized by an unexpected linear arrangement of clathrated di­chloro­methane molecules bound through type I and II halogen bonds. This rare phenomenon, observed in less than ten structures, was studied by coupled cluster-based energy decomposition.

Computing details

For all structures, data collection: MAR; cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: 'Mercury (Macrae et al., 2008), PLATON (Spek, 2009)'.

(IsI)

Crystal data

C13H10IN3O	Z = 4
Mr = 351.14	F(000) = 680
Triclinic, P1	Dx = 1.852 Mg m^−3
a = 10.0223 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1984 (3) Å	Cell parameters from 9164 reflections
c = 12.4505 (10) Å	θ = 3.2–25.8°
α = 109.836 (6)°	µ = 2.53 mm^−1
β = 101.250 (7)°	T = 297 K
γ = 97.494 (6)°	Block, colourless
V = 1259.58 (17) Å^3	0.50 × 0.20 × 0.10 mm

Data collection

MAR345 image plate diffractometer	4823 independent reflections
Radiation source: Rigaku UltraX 18 rotating anode	4533 reflections with I > 2σ(I)
Xenocs Fox3D mirror monochromator	Rint = 0.038
'110 images, ΔΦ 2.5° ' ' 55 images, ΔΦ 2.5° ' scans	θmax = 25.9°, θmin = 3.0°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→12
Tmin = 0.506, Tmax = 1.000	k = −13→13
18494 measured reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.5361P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
4823 reflections	Δρmax = 0.61 e Å^−3
325 parameters	Δρmin = −0.49 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
I1	0.75073 (2)	1.06523 (2)	1.05620 (2)	0.05001 (9)
C2	0.7127 (3)	0.8800 (2)	0.9233 (2)	0.0422 (6)
C3	0.8014 (3)	0.8525 (3)	0.8506 (3)	0.0463 (6)
H3	0.8794	0.9149	0.8622	0.056*
C4	0.7743 (3)	0.7321 (3)	0.7605 (3)	0.0461 (6)
H4	0.8343	0.7140	0.7115	0.055*
C5	0.6577 (3)	0.6373 (2)	0.7421 (2)	0.0404 (5)
C6	0.5709 (3)	0.6652 (3)	0.8180 (2)	0.0431 (6)
H6	0.4945	0.6022	0.8084	0.052*
C7	0.5973 (3)	0.7855 (3)	0.9074 (3)	0.0452 (6)
H7	0.5382	0.8037	0.9571	0.054*
C8	0.6343 (3)	0.5109 (3)	0.6467 (2)	0.0427 (6)
H8	0.7038	0.4920	0.6079	0.051*
N9	0.5218 (2)	0.4254 (2)	0.6146 (2)	0.0429 (5)
N10	0.5209 (2)	0.3089 (2)	0.5288 (2)	0.0409 (5)
H10	0.5944	0.2967	0.5043	0.049*
C11	0.4040 (2)	0.2133 (2)	0.4826 (2)	0.0381 (5)
O12	0.29362 (18)	0.22760 (19)	0.50696 (18)	0.0528 (5)
C13	0.4186 (3)	0.0880 (3)	0.3979 (2)	0.0370 (5)
C14	0.5060 (3)	0.0774 (3)	0.3231 (2)	0.0430 (6)
H14	0.5636	0.1510	0.3257	0.052*
C15	0.5064 (3)	−0.0444 (3)	0.2443 (3)	0.0512 (7)
H15	0.5655	−0.0501	0.1946	0.061*
N16	0.4267 (3)	−0.1539 (2)	0.2359 (2)	0.0530 (6)
C17	0.3456 (3)	−0.1429 (3)	0.3096 (3)	0.0485 (6)
H17	0.2909	−0.2185	0.3061	0.058*
C18	0.3372 (3)	−0.0261 (3)	0.3913 (2)	0.0422 (5)
H18	0.2783	−0.0239	0.4408	0.051*
I21	0.30846 (2)	0.57424 (2)	1.04111 (2)	0.05183 (9)
C22	0.2142 (3)	0.3858 (2)	0.9169 (2)	0.0424 (6)
C23	0.0896 (3)	0.3231 (3)	0.9238 (3)	0.0531 (7)
H23	0.0476	0.3640	0.9825	0.064*
C24	0.0278 (3)	0.1982 (3)	0.8420 (3)	0.0502 (6)
H24	−0.0562	0.1558	0.8461	0.060*
C25	0.0903 (3)	0.1362 (2)	0.7542 (2)	0.0399 (5)
C26	0.2140 (3)	0.2023 (3)	0.7478 (2)	0.0445 (6)
H26	0.2557	0.1625	0.6884	0.053*
C27	0.2759 (3)	0.3264 (3)	0.8282 (3)	0.0474 (6)
H27	0.3585	0.3698	0.8229	0.057*
C28	0.0245 (3)	0.0038 (3)	0.6719 (2)	0.0424 (6)
H28	−0.0653	−0.0317	0.6706	0.051*
N29	0.0874 (2)	−0.0646 (2)	0.6017 (2)	0.0421 (5)
N30	0.0096 (2)	−0.1865 (2)	0.5276 (2)	0.0415 (5)
H30	−0.0781	−0.2057	0.5219	0.050*
C31	0.0719 (2)	−0.2751 (2)	0.4644 (2)	0.0370 (5)
O32	0.19617 (19)	−0.25530 (18)	0.46947 (19)	0.0502 (4)
C33	−0.0217 (3)	−0.4033 (2)	0.3864 (2)	0.0369 (5)
C34	−0.1380 (3)	−0.4579 (3)	0.4125 (2)	0.0437 (6)
H34	−0.1664	−0.4118	0.4785	0.052*
C35	−0.2109 (3)	−0.5820 (3)	0.3387 (3)	0.0508 (6)
H35	−0.2879	−0.6176	0.3576	0.061*
N36	−0.1774 (3)	−0.6537 (2)	0.2421 (2)	0.0559 (6)
C37	−0.0679 (3)	−0.5995 (3)	0.2164 (3)	0.0551 (7)
H37	−0.0443	−0.6468	0.1481	0.066*
C38	0.0128 (3)	−0.4768 (3)	0.2852 (2)	0.0463 (6)
H38	0.0894	−0.4441	0.2639	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.05518 (13)	0.03297 (12)	0.04734 (13)	0.00340 (8)	0.01112 (9)	0.00046 (8)
C2	0.0450 (14)	0.0303 (12)	0.0396 (13)	0.0048 (10)	0.0042 (11)	0.0035 (10)
C3	0.0425 (13)	0.0338 (13)	0.0534 (16)	−0.0005 (10)	0.0108 (12)	0.0090 (11)
C4	0.0453 (14)	0.0381 (13)	0.0477 (15)	0.0049 (11)	0.0147 (11)	0.0072 (11)
C5	0.0408 (13)	0.0311 (12)	0.0405 (14)	0.0044 (10)	0.0058 (10)	0.0063 (11)
C6	0.0394 (13)	0.0342 (13)	0.0463 (15)	0.0013 (10)	0.0097 (11)	0.0066 (11)
C7	0.0444 (14)	0.0375 (13)	0.0466 (15)	0.0068 (11)	0.0162 (11)	0.0054 (11)
C8	0.0431 (13)	0.0344 (13)	0.0430 (14)	0.0057 (10)	0.0114 (11)	0.0059 (11)
N9	0.0409 (11)	0.0315 (11)	0.0432 (12)	0.0057 (9)	0.0089 (9)	−0.0002 (9)
N10	0.0348 (11)	0.0326 (11)	0.0451 (11)	0.0063 (9)	0.0115 (9)	0.0016 (9)
C11	0.0332 (11)	0.0343 (12)	0.0402 (13)	0.0049 (9)	0.0084 (10)	0.0073 (10)
O12	0.0364 (9)	0.0470 (10)	0.0622 (12)	0.0067 (8)	0.0183 (9)	0.0023 (9)
C13	0.0318 (11)	0.0329 (13)	0.0380 (13)	0.0046 (9)	0.0033 (9)	0.0071 (10)
C14	0.0462 (14)	0.0352 (13)	0.0427 (14)	0.0024 (10)	0.0159 (11)	0.0082 (11)
C15	0.0587 (16)	0.0409 (15)	0.0481 (16)	0.0066 (12)	0.0221 (13)	0.0061 (12)
N16	0.0642 (15)	0.0326 (11)	0.0477 (13)	0.0052 (11)	0.0149 (12)	−0.0012 (10)
C17	0.0506 (15)	0.0341 (13)	0.0506 (16)	−0.0011 (11)	0.0083 (12)	0.0097 (12)
C18	0.0394 (12)	0.0385 (13)	0.0432 (14)	0.0024 (10)	0.0120 (10)	0.0099 (11)
I21	0.05536 (13)	0.03383 (12)	0.04794 (13)	0.00371 (8)	0.00365 (9)	0.00012 (8)
C22	0.0434 (13)	0.0329 (13)	0.0386 (13)	0.0052 (10)	0.0038 (10)	0.0030 (10)
C23	0.0574 (17)	0.0446 (15)	0.0488 (16)	0.0067 (13)	0.0230 (13)	0.0035 (12)
C24	0.0482 (15)	0.0400 (14)	0.0519 (16)	−0.0013 (11)	0.0200 (12)	0.0041 (12)
C25	0.0389 (12)	0.0338 (13)	0.0384 (13)	0.0052 (10)	0.0071 (10)	0.0053 (10)
C26	0.0414 (13)	0.0383 (14)	0.0433 (14)	0.0050 (11)	0.0127 (11)	0.0026 (11)
C27	0.0404 (13)	0.0400 (14)	0.0504 (15)	0.0029 (11)	0.0117 (11)	0.0051 (11)
C28	0.0372 (12)	0.0358 (13)	0.0440 (14)	0.0013 (10)	0.0083 (10)	0.0058 (11)
N29	0.0357 (10)	0.0312 (11)	0.0433 (12)	−0.0009 (8)	0.0050 (9)	0.0001 (9)
N30	0.0306 (10)	0.0312 (11)	0.0490 (12)	−0.0001 (8)	0.0084 (9)	0.0018 (9)
C31	0.0343 (12)	0.0346 (12)	0.0388 (12)	0.0042 (9)	0.0112 (10)	0.0098 (10)
O32	0.0352 (9)	0.0441 (10)	0.0609 (11)	0.0022 (8)	0.0176 (8)	0.0061 (8)
C33	0.0345 (12)	0.0323 (13)	0.0407 (13)	0.0066 (10)	0.0083 (10)	0.0107 (11)
C34	0.0433 (13)	0.0350 (13)	0.0466 (14)	0.0019 (11)	0.0136 (11)	0.0090 (11)
C35	0.0497 (15)	0.0380 (14)	0.0552 (17)	−0.0019 (12)	0.0103 (13)	0.0118 (12)
N36	0.0615 (16)	0.0351 (12)	0.0516 (14)	0.0001 (11)	0.0039 (12)	0.0020 (10)
C37	0.0619 (18)	0.0457 (16)	0.0435 (15)	0.0087 (14)	0.0124 (13)	0.0007 (12)
C38	0.0450 (14)	0.0447 (14)	0.0422 (14)	0.0050 (11)	0.0140 (11)	0.0080 (11)

Geometric parameters (Å, º)

I1—C2	2.098 (3)	I21—C22	2.105 (3)
C2—C3	1.378 (4)	C22—C23	1.383 (4)
C2—C7	1.396 (4)	C22—C27	1.385 (4)
C3—C4	1.382 (4)	C23—C24	1.392 (4)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.398 (4)	C24—C25	1.391 (4)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.393 (4)	C25—C26	1.390 (4)
C5—C8	1.460 (4)	C25—C28	1.461 (4)
C6—C7	1.377 (4)	C26—C27	1.381 (4)
C6—H6	0.9300	C26—H26	0.9300
C7—H7	0.9300	C27—H27	0.9300
C8—N9	1.276 (4)	C28—N29	1.278 (4)
C8—H8	0.9300	C28—H28	0.9300
N9—N10	1.375 (3)	N29—N30	1.382 (3)
N10—C11	1.358 (3)	N30—C31	1.348 (3)
N10—H10	0.8600	N30—H30	0.8600
C11—O12	1.219 (3)	C31—O32	1.222 (3)
C11—C13	1.487 (3)	C31—C33	1.494 (3)
C13—C14	1.386 (4)	C33—C38	1.388 (4)
C13—C18	1.391 (4)	C33—C34	1.391 (4)
C14—C15	1.384 (4)	C34—C35	1.384 (4)
C14—H14	0.9300	C34—H34	0.9300
C15—N16	1.333 (4)	C35—N36	1.332 (4)
C15—H15	0.9300	C35—H35	0.9300
N16—C17	1.326 (4)	N36—C37	1.330 (4)
C17—C18	1.382 (4)	C37—C38	1.385 (4)
C17—H17	0.9300	C37—H37	0.9300
C18—H18	0.9300	C38—H38	0.9300
C3—C2—C7	120.0 (2)	C23—C22—C27	120.6 (2)
C3—C2—I1	119.7 (2)	C23—C22—I21	119.4 (2)
C7—C2—I1	120.3 (2)	C27—C22—I21	120.0 (2)
C2—C3—C4	120.0 (3)	C22—C23—C24	119.4 (3)
C2—C3—H3	120.0	C22—C23—H23	120.3
C4—C3—H3	120.0	C24—C23—H23	120.3
C3—C4—C5	120.7 (3)	C25—C24—C23	120.7 (3)
C3—C4—H4	119.7	C25—C24—H24	119.7
C5—C4—H4	119.7	C23—C24—H24	119.7
C6—C5—C4	118.8 (2)	C26—C25—C24	118.8 (2)
C6—C5—C8	122.4 (2)	C26—C25—C28	122.0 (2)
C4—C5—C8	118.8 (2)	C24—C25—C28	119.2 (2)
C7—C6—C5	120.6 (2)	C27—C26—C25	120.9 (3)
C7—C6—H6	119.7	C27—C26—H26	119.5
C5—C6—H6	119.7	C25—C26—H26	119.5
C6—C7—C2	120.0 (2)	C26—C27—C22	119.6 (3)
C6—C7—H7	120.0	C26—C27—H27	120.2
C2—C7—H7	120.0	C22—C27—H27	120.2
N9—C8—C5	122.5 (2)	N29—C28—C25	121.6 (2)
N9—C8—H8	118.8	N29—C28—H28	119.2
C5—C8—H8	118.8	C25—C28—H28	119.2
C8—N9—N10	114.7 (2)	C28—N29—N30	114.4 (2)
C11—N10—N9	120.0 (2)	C31—N30—N29	119.7 (2)
C11—N10—H10	120.0	C31—N30—H30	120.2
N9—N10—H10	120.0	N29—N30—H30	120.2
O12—C11—N10	123.2 (2)	O32—C31—N30	123.8 (2)
O12—C11—C13	121.5 (2)	O32—C31—C33	120.8 (2)
N10—C11—C13	115.3 (2)	N30—C31—C33	115.4 (2)
C14—C13—C18	117.6 (2)	C38—C33—C34	117.3 (2)
C14—C13—C11	124.3 (2)	C38—C33—C31	118.7 (2)
C18—C13—C11	118.1 (2)	C34—C33—C31	123.9 (2)
C15—C14—C13	119.1 (2)	C35—C34—C33	119.0 (3)
C15—C14—H14	120.5	C35—C34—H34	120.5
C13—C14—H14	120.5	C33—C34—H34	120.5
N16—C15—C14	123.6 (3)	N36—C35—C34	124.0 (3)
N16—C15—H15	118.2	N36—C35—H35	118.0
C14—C15—H15	118.2	C34—C35—H35	118.0
C17—N16—C15	116.8 (2)	C37—N36—C35	116.6 (3)
N16—C17—C18	124.2 (3)	N36—C37—C38	123.9 (3)
N16—C17—H17	117.9	N36—C37—H37	118.1
C18—C17—H17	117.9	C38—C37—H37	118.1
C17—C18—C13	118.7 (2)	C37—C38—C33	119.2 (3)
C17—C18—H18	120.6	C37—C38—H38	120.4
C13—C18—H18	120.6	C33—C38—H38	120.4
C7—C2—C3—C4	1.3 (4)	C27—C22—C23—C24	1.3 (5)
I1—C2—C3—C4	−177.9 (2)	I21—C22—C23—C24	−179.6 (2)
C2—C3—C4—C5	−0.1 (4)	C22—C23—C24—C25	0.2 (5)
C3—C4—C5—C6	−1.5 (4)	C23—C24—C25—C26	−1.5 (5)
C3—C4—C5—C8	−179.2 (3)	C23—C24—C25—C28	178.3 (3)
C4—C5—C6—C7	1.9 (4)	C24—C25—C26—C27	1.3 (4)
C8—C5—C6—C7	179.6 (3)	C28—C25—C26—C27	−178.5 (3)
C5—C6—C7—C2	−0.8 (4)	C25—C26—C27—C22	0.2 (5)
C3—C2—C7—C6	−0.9 (4)	C23—C22—C27—C26	−1.5 (4)
I1—C2—C7—C6	178.3 (2)	I21—C22—C27—C26	179.4 (2)
C6—C5—C8—N9	11.5 (4)	C26—C25—C28—N29	10.7 (4)
C4—C5—C8—N9	−170.9 (3)	C24—C25—C28—N29	−169.1 (3)
C5—C8—N9—N10	−176.0 (2)	C25—C28—N29—N30	−178.5 (2)
C8—N9—N10—C11	−176.1 (2)	C28—N29—N30—C31	−168.7 (2)
N9—N10—C11—O12	5.6 (4)	N29—N30—C31—O32	1.2 (4)
N9—N10—C11—C13	−175.1 (2)	N29—N30—C31—C33	−179.5 (2)
O12—C11—C13—C14	147.1 (3)	O32—C31—C33—C38	−28.3 (4)
N10—C11—C13—C14	−32.2 (4)	N30—C31—C33—C38	152.5 (3)
O12—C11—C13—C18	−31.5 (4)	O32—C31—C33—C34	147.7 (3)
N10—C11—C13—C18	149.2 (2)	N30—C31—C33—C34	−31.5 (4)
C18—C13—C14—C15	1.3 (4)	C38—C33—C34—C35	1.3 (4)
C11—C13—C14—C15	−177.3 (3)	C31—C33—C34—C35	−174.8 (3)
C13—C14—C15—N16	−0.1 (5)	C33—C34—C35—N36	−0.6 (5)
C14—C15—N16—C17	−1.3 (5)	C34—C35—N36—C37	−0.9 (5)
C15—N16—C17—C18	1.4 (5)	C35—N36—C37—C38	1.8 (5)
N16—C17—C18—C13	−0.2 (5)	N36—C37—C38—C33	−1.1 (5)
C14—C13—C18—C17	−1.2 (4)	C34—C33—C38—C37	−0.4 (4)
C11—C13—C18—C17	177.5 (2)	C31—C33—C38—C37	175.8 (3)

(HyI)

Crystal data

C15H11IN4	Dx = 1.711 Mg m^−3
Mr = 374.18	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41	Cell parameters from 6953 reflections
a = 15.0197 (4) Å	θ = 3.4–25.1°
c = 12.8791 (6) Å	µ = 2.20 mm^−1
V = 2905.40 (19) Å^3	T = 297 K
Z = 8	Needle, yellow
F(000) = 1456	0.50 × 0.02 × 0.02 mm

Data collection

MAR345 image plate diffractometer	2616 independent reflections
Radiation source: Rigaku UltraX 18 rotating anode	2374 reflections with I > 2σ(I)
Xenocs Fox3D mirror monochromator	Rint = 0.040
130 images, ΔΦ 2.0° scans	θmax = 25.3°, θmin = 3.4°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −18→17
Tmin = 0.905, Tmax = 1.000	k = −18→18
13780 measured reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.033P)^2 + 7.2193P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 1.17 e Å^−3
2616 reflections	Δρmin = −0.60 e Å^−3
181 parameters	Absolute structure: Flack x determined using 1029 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: 0.050 (12)

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
I1	1.19416 (3)	0.61072 (5)	0.73045 (5)	0.0820 (3)
C2	1.0607 (5)	0.6259 (5)	0.6871 (6)	0.0496 (18)
C3	1.0001 (5)	0.6518 (6)	0.7621 (6)	0.0565 (19)
H3	1.0190	0.6649	0.8292	0.068*
C4	0.9114 (5)	0.6577 (6)	0.7359 (8)	0.0574 (19)
H4	0.8704	0.6742	0.7864	0.069*
C5	0.8818 (5)	0.6397 (5)	0.6362 (5)	0.0416 (15)
C6	0.9454 (5)	0.6171 (5)	0.5618 (5)	0.0472 (16)
H6	0.9275	0.6067	0.4937	0.057*
C7	1.0338 (5)	0.6100 (5)	0.5875 (6)	0.0496 (17)
H7	1.0754	0.5943	0.5371	0.059*
C8	0.7879 (5)	0.6436 (5)	0.6154 (5)	0.0454 (16)
H8	0.7499	0.6585	0.6697	0.054*
N9	0.7538 (4)	0.6278 (4)	0.5274 (4)	0.0450 (13)
N10	0.6604 (4)	0.6325 (4)	0.5279 (4)	0.0462 (14)
C11	0.6275 (5)	0.6246 (5)	0.4349 (5)	0.0437 (16)
N12	0.6754 (4)	0.6196 (4)	0.3460 (5)	0.0507 (15)
H12	0.7323	0.6205	0.3529	0.061*
N13	0.6442 (5)	0.6132 (5)	0.2473 (5)	0.0622 (17)
C14	0.5585 (5)	0.6135 (6)	0.2388 (7)	0.065 (2)
H14	0.5352	0.6098	0.1721	0.078*
C15	0.4964 (5)	0.6188 (5)	0.3220 (6)	0.0556 (19)
C16	0.4052 (6)	0.6166 (7)	0.3080 (8)	0.076 (3)
H16	0.3818	0.6143	0.2412	0.092*
C17	0.3499 (7)	0.6177 (8)	0.3907 (10)	0.090 (3)
H17	0.2886	0.6154	0.3804	0.108*
C18	0.3838 (7)	0.6220 (8)	0.4912 (10)	0.092 (3)
H18	0.3453	0.6235	0.5477	0.111*
C19	0.4744 (5)	0.6243 (6)	0.5070 (7)	0.068 (2)
H19	0.4975	0.6263	0.5740	0.081*
C20	0.5304 (5)	0.6234 (5)	0.4221 (6)	0.0482 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0452 (3)	0.1142 (5)	0.0865 (4)	0.0027 (3)	−0.0038 (3)	0.0152 (4)
C2	0.044 (4)	0.047 (4)	0.058 (4)	−0.002 (3)	0.000 (3)	0.008 (3)
C3	0.054 (4)	0.070 (5)	0.045 (4)	0.002 (4)	−0.006 (3)	0.003 (4)
C4	0.055 (4)	0.077 (5)	0.040 (4)	0.010 (3)	0.000 (4)	−0.003 (4)
C5	0.048 (4)	0.044 (4)	0.033 (3)	0.004 (3)	0.002 (3)	0.001 (3)
C6	0.057 (4)	0.048 (4)	0.036 (3)	−0.003 (3)	0.002 (3)	−0.002 (3)
C7	0.049 (4)	0.051 (4)	0.049 (4)	−0.002 (3)	0.012 (3)	0.001 (3)
C8	0.049 (4)	0.054 (4)	0.033 (3)	0.004 (3)	0.007 (3)	0.003 (3)
N9	0.043 (3)	0.056 (4)	0.035 (3)	0.002 (3)	0.000 (2)	0.002 (2)
N10	0.043 (3)	0.059 (4)	0.037 (3)	0.000 (3)	0.004 (3)	−0.002 (3)
C11	0.050 (4)	0.046 (4)	0.035 (4)	−0.002 (3)	0.004 (3)	−0.007 (3)
N12	0.048 (3)	0.069 (4)	0.035 (3)	0.000 (3)	−0.002 (3)	−0.007 (3)
N13	0.072 (4)	0.083 (5)	0.031 (3)	−0.001 (3)	−0.002 (3)	−0.006 (3)
C14	0.068 (5)	0.086 (6)	0.040 (4)	0.002 (4)	−0.010 (5)	−0.008 (4)
C15	0.057 (5)	0.062 (5)	0.048 (4)	−0.006 (4)	−0.011 (4)	−0.011 (4)
C16	0.063 (6)	0.088 (7)	0.078 (6)	0.003 (5)	−0.021 (5)	−0.022 (5)
C17	0.051 (5)	0.117 (9)	0.102 (9)	−0.005 (5)	−0.010 (6)	−0.030 (7)
C18	0.064 (6)	0.132 (9)	0.081 (7)	0.001 (6)	0.018 (5)	−0.031 (8)
C19	0.049 (4)	0.095 (6)	0.059 (6)	0.003 (4)	0.003 (4)	−0.014 (4)
C20	0.049 (4)	0.050 (4)	0.046 (4)	0.001 (3)	−0.001 (3)	−0.009 (3)

Geometric parameters (Å, º)

I1—C2	2.093 (7)	C11—C20	1.469 (10)
C2—C7	1.367 (11)	N12—N13	1.359 (9)
C2—C3	1.383 (11)	N12—H12	0.8600
C3—C4	1.377 (11)	N13—C14	1.291 (10)
C3—H3	0.9300	C14—C15	1.422 (12)
C4—C5	1.386 (12)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.382 (12)
C5—C6	1.394 (10)	C15—C20	1.388 (11)
C5—C8	1.438 (10)	C16—C17	1.351 (15)
C6—C7	1.374 (10)	C16—H16	0.9300
C6—H6	0.9300	C17—C18	1.393 (17)
C7—H7	0.9300	C17—H17	0.9300
C8—N9	1.265 (9)	C18—C19	1.375 (13)
C8—H8	0.9300	C18—H18	0.9300
N9—N10	1.405 (9)	C19—C20	1.381 (11)
N10—C11	1.300 (9)	C19—H19	0.9300
C11—N12	1.353 (9)
C7—C2—C3	120.7 (7)	C11—N12—N13	127.8 (6)
C7—C2—I1	120.9 (6)	C11—N12—H12	116.1
C3—C2—I1	118.3 (6)	N13—N12—H12	116.1
C4—C3—C2	118.9 (8)	C14—N13—N12	115.0 (7)
C4—C3—H3	120.5	N13—C14—C15	126.2 (8)
C2—C3—H3	120.5	N13—C14—H14	116.9
C3—C4—C5	121.6 (8)	C15—C14—H14	116.9
C3—C4—H4	119.2	C16—C15—C20	119.1 (8)
C5—C4—H4	119.2	C16—C15—C14	123.4 (8)
C4—C5—C6	117.7 (7)	C20—C15—C14	117.5 (7)
C4—C5—C8	118.7 (6)	C17—C16—C15	120.5 (9)
C6—C5—C8	123.6 (6)	C17—C16—H16	119.7
C7—C6—C5	121.0 (7)	C15—C16—H16	119.7
C7—C6—H6	119.5	C16—C17—C18	120.5 (9)
C5—C6—H6	119.5	C16—C17—H17	119.8
C2—C7—C6	119.9 (7)	C18—C17—H17	119.8
C2—C7—H7	120.1	C19—C18—C17	120.1 (10)
C6—C7—H7	120.1	C19—C18—H18	120.0
N9—C8—C5	123.8 (6)	C17—C18—H18	120.0
N9—C8—H8	118.1	C18—C19—C20	119.0 (9)
C5—C8—H8	118.1	C18—C19—H19	120.5
C8—N9—N10	113.0 (6)	C20—C19—H19	120.5
C11—N10—N9	111.8 (5)	C19—C20—C15	120.9 (7)
N10—C11—N12	125.6 (7)	C19—C20—C11	121.1 (7)
N10—C11—C20	118.8 (6)	C15—C20—C11	118.0 (7)
N12—C11—C20	115.6 (6)
C7—C2—C3—C4	2.6 (12)	N12—N13—C14—C15	−0.6 (13)
I1—C2—C3—C4	−176.8 (6)	N13—C14—C15—C16	−178.3 (9)
C2—C3—C4—C5	−0.9 (13)	N13—C14—C15—C20	−0.7 (14)
C3—C4—C5—C6	−1.5 (12)	C20—C15—C16—C17	−0.8 (15)
C3—C4—C5—C8	177.5 (7)	C14—C15—C16—C17	176.8 (10)
C4—C5—C6—C7	2.2 (11)	C15—C16—C17—C18	0.7 (18)
C8—C5—C6—C7	−176.6 (7)	C16—C17—C18—C19	−0.8 (19)
C3—C2—C7—C6	−1.9 (12)	C17—C18—C19—C20	0.9 (17)
I1—C2—C7—C6	177.5 (5)	C18—C19—C20—C15	−1.1 (14)
C5—C6—C7—C2	−0.6 (11)	C18—C19—C20—C11	−179.3 (8)
C4—C5—C8—N9	−179.6 (7)	C16—C15—C20—C19	1.0 (13)
C6—C5—C8—N9	−0.7 (11)	C14—C15—C20—C19	−176.8 (8)
C5—C8—N9—N10	177.6 (6)	C16—C15—C20—C11	179.3 (8)
C8—N9—N10—C11	173.8 (7)	C14—C15—C20—C11	1.5 (11)
N9—N10—C11—N12	−4.9 (11)	N10—C11—C20—C19	−4.4 (12)
N9—N10—C11—C20	176.8 (6)	N12—C11—C20—C19	177.2 (8)
N10—C11—N12—N13	−178.5 (8)	N10—C11—C20—C15	177.3 (8)
C20—C11—N12—N13	−0.3 (11)	N12—C11—C20—C15	−1.1 (10)
C11—N12—N13—C14	1.1 (12)

(HyBr)

Crystal data

C15H11BrN4	F(000) = 656
Mr = 327.19	Dx = 1.626 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.8761 (7) Å	Cell parameters from 6643 reflections
b = 4.0269 (2) Å	θ = 3.6–26.1°
c = 23.1830 (12) Å	µ = 3.07 mm^−1
β = 105.810 (5)°	T = 297 K
V = 1336.24 (12) Å^3	Rod, yellow
Z = 4	0.50 × 0.12 × 0.07 mm

Data collection

MAR345 image plate diffractometer	2600 independent reflections
Radiation source: Rigaku UltraX 18 rotating anode	2284 reflections with I > 2σ(I)
Xenocs Fox3D mirror monochromator	Rint = 0.049
135 images, ΔΦ 2.0° scans	θmax = 26.2°, θmin = 3.5°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −18→18
Tmin = 0.378, Tmax = 1.000	k = −4→4
12533 measured reflections	l = −28→28

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0599P)^2 + 0.5605P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2600 reflections	Δρmax = 0.41 e Å^−3
181 parameters	Δρmin = −0.49 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
Br1	0.96756 (2)	0.58076 (10)	0.82238 (2)	0.07469 (18)
C2	0.84000 (18)	0.5188 (7)	0.78026 (12)	0.0501 (6)
C3	0.78232 (19)	0.3540 (7)	0.80791 (11)	0.0524 (6)
H3	0.8061	0.2669	0.8462	0.063*
C4	0.68893 (19)	0.3190 (7)	0.77837 (11)	0.0511 (6)
H4	0.6497	0.2072	0.7969	0.061*
C5	0.65269 (18)	0.4500 (6)	0.72087 (11)	0.0445 (5)
C6	0.71300 (19)	0.6132 (6)	0.69396 (11)	0.0511 (6)
H6	0.6900	0.6986	0.6555	0.061*
C7	0.80671 (19)	0.6507 (7)	0.72344 (11)	0.0541 (6)
H7	0.8465	0.7625	0.7053	0.065*
C8	0.55325 (19)	0.4074 (6)	0.69022 (11)	0.0482 (6)
H8	0.5164	0.2807	0.7084	0.058*
N9	0.51604 (14)	0.5390 (5)	0.63948 (9)	0.0471 (5)
N10	0.42153 (14)	0.4587 (5)	0.61789 (9)	0.0479 (5)
C11	0.38520 (16)	0.5713 (6)	0.56375 (10)	0.0416 (5)
N12	0.43243 (13)	0.7541 (6)	0.53221 (9)	0.0473 (5)
H12	0.4890	0.8072	0.5505	0.057*
N13	0.39918 (16)	0.8617 (6)	0.47452 (9)	0.0523 (5)
C14	0.31429 (18)	0.7856 (7)	0.44714 (11)	0.0512 (6)
H14	0.2911	0.8534	0.4075	0.061*
C15	0.25314 (17)	0.6031 (6)	0.47371 (11)	0.0466 (5)
C16	0.16031 (19)	0.5311 (7)	0.44273 (13)	0.0573 (6)
H16	0.1371	0.5946	0.4029	0.069*
C17	0.10373 (19)	0.3672 (8)	0.47111 (15)	0.0645 (7)
H17	0.0418	0.3237	0.4507	0.077*
C18	0.13881 (19)	0.2659 (8)	0.53040 (14)	0.0629 (7)
H18	0.1000	0.1547	0.5493	0.076*
C19	0.22996 (19)	0.3279 (7)	0.56127 (12)	0.0524 (6)
H19	0.2529	0.2568	0.6007	0.063*
C20	0.28799 (16)	0.4984 (6)	0.53313 (11)	0.0426 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0510 (2)	0.0902 (3)	0.0719 (2)	−0.00186 (13)	−0.00184 (15)	−0.00538 (16)
C2	0.0473 (13)	0.0529 (13)	0.0462 (13)	0.0038 (10)	0.0059 (10)	−0.0078 (11)
C3	0.0571 (14)	0.0575 (14)	0.0387 (11)	0.0056 (11)	0.0066 (10)	0.0029 (11)
C4	0.0567 (14)	0.0560 (14)	0.0420 (12)	0.0014 (11)	0.0156 (10)	0.0053 (11)
C5	0.0474 (13)	0.0466 (12)	0.0382 (11)	0.0028 (10)	0.0093 (9)	−0.0022 (10)
C6	0.0571 (14)	0.0561 (14)	0.0382 (11)	0.0000 (11)	0.0101 (10)	0.0064 (10)
C7	0.0528 (14)	0.0621 (15)	0.0468 (13)	−0.0054 (12)	0.0125 (11)	0.0026 (12)
C8	0.0506 (13)	0.0518 (14)	0.0430 (12)	−0.0001 (10)	0.0144 (10)	0.0005 (10)
N9	0.0420 (10)	0.0555 (11)	0.0422 (10)	−0.0012 (9)	0.0084 (8)	−0.0016 (9)
N10	0.0436 (11)	0.0569 (12)	0.0428 (10)	−0.0019 (9)	0.0112 (9)	−0.0012 (9)
C11	0.0412 (11)	0.0456 (12)	0.0399 (11)	0.0018 (9)	0.0143 (9)	−0.0043 (9)
N12	0.0386 (10)	0.0598 (12)	0.0444 (10)	−0.0038 (9)	0.0128 (8)	0.0007 (9)
N13	0.0549 (12)	0.0604 (13)	0.0439 (10)	−0.0019 (10)	0.0176 (9)	0.0025 (10)
C14	0.0521 (14)	0.0599 (15)	0.0398 (11)	0.0039 (12)	0.0097 (10)	0.0034 (11)
C15	0.0429 (12)	0.0480 (13)	0.0483 (12)	0.0034 (9)	0.0113 (10)	−0.0062 (10)
C16	0.0457 (14)	0.0657 (16)	0.0526 (14)	0.0053 (12)	0.0000 (11)	−0.0050 (13)
C17	0.0383 (13)	0.0728 (18)	0.0768 (18)	−0.0053 (12)	0.0062 (12)	−0.0149 (15)
C18	0.0489 (14)	0.0689 (18)	0.0757 (18)	−0.0134 (13)	0.0249 (13)	−0.0090 (15)
C19	0.0524 (14)	0.0560 (14)	0.0520 (13)	−0.0067 (12)	0.0195 (11)	−0.0051 (12)
C20	0.0401 (11)	0.0437 (11)	0.0453 (12)	0.0009 (9)	0.0137 (9)	−0.0064 (10)

Geometric parameters (Å, º)

Br1—C2	1.899 (3)	C11—C20	1.457 (3)
C2—C3	1.374 (4)	N12—N13	1.364 (3)
C2—C7	1.381 (4)	N12—H12	0.8600
C3—C4	1.379 (4)	N13—C14	1.286 (3)
C3—H3	0.9300	C14—C15	1.433 (4)
C4—C5	1.398 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C20	1.398 (4)
C5—C6	1.390 (4)	C15—C16	1.402 (4)
C5—C8	1.466 (4)	C16—C17	1.371 (4)
C6—C7	1.383 (4)	C16—H16	0.9300
C6—H6	0.9300	C17—C18	1.392 (5)
C7—H7	0.9300	C17—H17	0.9300
C8—N9	1.271 (3)	C18—C19	1.373 (4)
C8—H8	0.9300	C18—H18	0.9300
N9—N10	1.396 (3)	C19—C20	1.396 (4)
N10—C11	1.305 (3)	C19—H19	0.9300
C11—N12	1.360 (3)
C3—C2—C7	121.6 (2)	C11—N12—N13	126.6 (2)
C3—C2—Br1	119.1 (2)	C11—N12—H12	116.7
C7—C2—Br1	119.2 (2)	N13—N12—H12	116.7
C2—C3—C4	119.4 (2)	C14—N13—N12	116.9 (2)
C2—C3—H3	120.3	N13—C14—C15	124.3 (2)
C4—C3—H3	120.3	N13—C14—H14	117.9
C3—C4—C5	120.7 (2)	C15—C14—H14	117.9
C3—C4—H4	119.7	C20—C15—C16	119.4 (2)
C5—C4—H4	119.7	C20—C15—C14	118.0 (2)
C6—C5—C4	118.6 (2)	C16—C15—C14	122.5 (2)
C6—C5—C8	121.8 (2)	C17—C16—C15	120.1 (3)
C4—C5—C8	119.6 (2)	C17—C16—H16	119.9
C7—C6—C5	121.1 (2)	C15—C16—H16	119.9
C7—C6—H6	119.4	C16—C17—C18	120.1 (3)
C5—C6—H6	119.4	C16—C17—H17	120.0
C2—C7—C6	118.7 (2)	C18—C17—H17	120.0
C2—C7—H7	120.6	C19—C18—C17	120.8 (3)
C6—C7—H7	120.6	C19—C18—H18	119.6
N9—C8—C5	121.8 (2)	C17—C18—H18	119.6
N9—C8—H8	119.1	C18—C19—C20	119.6 (3)
C5—C8—H8	119.1	C18—C19—H19	120.2
C8—N9—N10	112.2 (2)	C20—C19—H19	120.2
C11—N10—N9	112.15 (19)	C19—C20—C15	119.9 (2)
N10—C11—N12	124.5 (2)	C19—C20—C11	122.0 (2)
N10—C11—C20	119.6 (2)	C15—C20—C11	118.2 (2)
N12—C11—C20	115.9 (2)
C7—C2—C3—C4	0.0 (4)	N12—N13—C14—C15	1.3 (4)
Br1—C2—C3—C4	177.6 (2)	N13—C14—C15—C20	−0.5 (4)
C2—C3—C4—C5	−0.1 (4)	N13—C14—C15—C16	178.6 (3)
C3—C4—C5—C6	0.6 (4)	C20—C15—C16—C17	1.7 (4)
C3—C4—C5—C8	179.6 (2)	C14—C15—C16—C17	−177.4 (3)
C4—C5—C6—C7	−0.9 (4)	C15—C16—C17—C18	−1.3 (4)
C8—C5—C6—C7	−179.9 (2)	C16—C17—C18—C19	0.0 (5)
C3—C2—C7—C6	−0.3 (4)	C17—C18—C19—C20	0.8 (4)
Br1—C2—C7—C6	−177.9 (2)	C18—C19—C20—C15	−0.3 (4)
C5—C6—C7—C2	0.8 (4)	C18—C19—C20—C11	179.9 (2)
C6—C5—C8—N9	−5.4 (4)	C16—C15—C20—C19	−0.9 (4)
C4—C5—C8—N9	175.7 (2)	C14—C15—C20—C19	178.2 (2)
C5—C8—N9—N10	178.3 (2)	C16—C15—C20—C11	178.8 (2)
C8—N9—N10—C11	−174.8 (2)	C14—C15—C20—C11	−2.0 (3)
N9—N10—C11—N12	−1.8 (3)	N10—C11—C20—C19	4.1 (4)
N9—N10—C11—C20	177.41 (19)	N12—C11—C20—C19	−176.7 (2)
N10—C11—N12—N13	176.1 (2)	N10—C11—C20—C15	−175.6 (2)
C20—C11—N12—N13	−3.1 (3)	N12—C11—C20—C15	3.6 (3)
C11—N12—N13—C14	0.7 (4)

(HyOH)

Crystal data

C15H12N4O·CH2Cl2	F(000) = 1440
Mr = 349.21	Dx = 1.445 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.51859 (16) Å	Cell parameters from 11622 reflections
b = 15.70955 (19) Å	θ = 2.9–26.1°
c = 21.6869 (3) Å	µ = 0.41 mm^−1
β = 98.0651 (15)°	T = 297 K
V = 3210.83 (8) Å^3	Block, yellow
Z = 8	0.5 × 0.5 × 0.32 mm

Data collection

MAR345 image plate diffractometer	6290 independent reflections
Radiation source: Rigaku UltraX 18 rotating anode	5748 reflections with I > 2σ(I)
Xenocs Fox3D mirror monochromator	Rint = 0.020
180 images, ΔΦ 1.0° scans	θmax = 26.2°, θmin = 3.1°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.875, Tmax = 1.000	k = −18→19
22125 measured reflections	l = −26→26

Refinement

Refinement on F^2	0 restraints
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) = 0.136	w = 1/[σ^2(Fo^2) + (0.0645P)^2 + 4.0926P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
6290 reflections	Δρmax = 1.24 e Å^−3
417 parameters	Δρmin = −1.13 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
O1	0.35051 (18)	0.88621 (10)	0.74921 (7)	0.0320 (4)
H1	0.3749	0.8969	0.7862	0.048*
C2	0.4026 (2)	0.80946 (13)	0.73563 (9)	0.0234 (4)
C3	0.4931 (2)	0.76235 (13)	0.77871 (9)	0.0247 (4)
H3	0.5223	0.7842	0.8183	0.030*
C4	0.5396 (2)	0.68304 (13)	0.76265 (9)	0.0263 (4)
H4	0.6008	0.6522	0.7916	0.032*
C5	0.4965 (2)	0.64837 (13)	0.70372 (9)	0.0231 (4)
C6	0.4085 (2)	0.69724 (13)	0.66047 (9)	0.0248 (4)
H6	0.3803	0.6758	0.6207	0.030*
C7	0.3627 (2)	0.77691 (14)	0.67586 (10)	0.0276 (4)
H7	0.3052	0.8089	0.6463	0.033*
C8	0.5489 (2)	0.56484 (13)	0.68857 (10)	0.0264 (4)
H8	0.6214	0.5399	0.7158	0.032*
N9	0.49832 (19)	0.52481 (10)	0.63907 (8)	0.0237 (4)
N10	0.56612 (18)	0.44685 (10)	0.63295 (8)	0.0228 (4)
C11	0.5176 (2)	0.40816 (12)	0.58054 (9)	0.0203 (4)
N12	0.40802 (18)	0.43875 (11)	0.53938 (8)	0.0224 (4)
H12	0.3727	0.4868	0.5484	0.027*
N13	0.34844 (19)	0.40097 (11)	0.48524 (8)	0.0254 (4)
C14	0.4020 (2)	0.32918 (14)	0.47156 (9)	0.0272 (4)
H14	0.3616	0.3021	0.4352	0.033*
C15	0.5203 (2)	0.28791 (13)	0.50863 (9)	0.0237 (4)
C16	0.5757 (3)	0.21036 (14)	0.49132 (10)	0.0303 (5)
H16	0.5342	0.1827	0.4554	0.036*
C17	0.6916 (3)	0.17497 (14)	0.52730 (11)	0.0328 (5)
H17	0.7286	0.1236	0.5156	0.039*
C18	0.7537 (2)	0.21613 (14)	0.58152 (10)	0.0306 (5)
H18	0.8325	0.1922	0.6055	0.037*
C19	0.6992 (2)	0.29181 (13)	0.59974 (9)	0.0252 (4)
H19	0.7409	0.3187	0.6359	0.030*
C20	0.5807 (2)	0.32819 (12)	0.56363 (9)	0.0206 (4)
O21	0.19608 (16)	0.09394 (9)	0.24541 (7)	0.0283 (3)
H21	0.1518	0.0748	0.2132	0.042*
C22	0.1322 (2)	0.16628 (12)	0.26169 (9)	0.0222 (4)
C23	−0.0055 (2)	0.18861 (13)	0.23644 (9)	0.0260 (4)
H23	−0.0581	0.1530	0.2077	0.031*
C24	−0.0642 (2)	0.26395 (13)	0.25427 (9)	0.0253 (4)
H24	−0.1560	0.2785	0.2370	0.030*
C25	0.0117 (2)	0.31825 (13)	0.29754 (9)	0.0222 (4)
C26	0.1491 (2)	0.29437 (13)	0.32291 (9)	0.0260 (4)
H26	0.2015	0.3296	0.3521	0.031*
C27	0.2087 (2)	0.21954 (13)	0.30554 (9)	0.0259 (4)
H27	0.3002	0.2046	0.3232	0.031*
C28	−0.0492 (2)	0.39912 (13)	0.31370 (9)	0.0235 (4)
H28	−0.1386	0.4148	0.2940	0.028*
N29	0.01772 (19)	0.44894 (11)	0.35429 (8)	0.0237 (4)
N30	−0.05494 (18)	0.52465 (10)	0.36330 (8)	0.0222 (4)
C31	0.0001 (2)	0.56323 (12)	0.41469 (9)	0.0207 (4)
N32	0.11503 (18)	0.53201 (11)	0.45289 (8)	0.0225 (4)
H32	0.1523	0.4861	0.4409	0.027*
N33	0.17699 (18)	0.56593 (11)	0.50801 (8)	0.0240 (4)
C34	0.1210 (2)	0.63445 (13)	0.52629 (9)	0.0244 (4)
H34	0.1602	0.6576	0.5643	0.029*
C35	0.0014 (2)	0.67761 (13)	0.49171 (9)	0.0227 (4)
C36	−0.0508 (2)	0.75374 (14)	0.51304 (10)	0.0283 (4)
H36	−0.0112	0.7762	0.5512	0.034*
C37	−0.1611 (2)	0.79547 (14)	0.47735 (11)	0.0311 (5)
H37	−0.1943	0.8469	0.4909	0.037*
C38	−0.2226 (2)	0.76034 (14)	0.42077 (10)	0.0297 (5)
H38	−0.2972	0.7886	0.3969	0.036*
C39	−0.1746 (2)	0.68448 (13)	0.39975 (9)	0.0250 (4)
H39	−0.2181	0.6610	0.3625	0.030*
C40	−0.0595 (2)	0.64259 (12)	0.43470 (9)	0.0210 (4)
C41	0.0803 (3)	0.96999 (17)	0.65255 (14)	0.0452 (6)
H41A	−0.0011	0.9421	0.6660	0.054*
H41B	0.1655	0.9427	0.6733	0.054*
Cl42	0.08127 (9)	1.07697 (6)	0.67309 (4)	0.0650 (3)
Cl43	0.07280 (8)	0.95924 (7)	0.57106 (4)	0.0715 (3)
C44	0.4013 (3)	−0.0070 (2)	0.35576 (14)	0.0489 (7)
H44A	0.3983	0.0277	0.3186	0.059*
H44B	0.3678	−0.0636	0.3431	0.059*
Cl45	0.57710 (7)	−0.01353 (5)	0.39314 (4)	0.0554 (2)
Cl46	0.28942 (8)	0.03725 (5)	0.40485 (4)	0.0527 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0422 (9)	0.0242 (8)	0.0260 (7)	0.0104 (7)	−0.0079 (7)	−0.0064 (6)
C2	0.0260 (10)	0.0189 (9)	0.0244 (10)	0.0007 (8)	0.0004 (8)	−0.0015 (8)
C3	0.0306 (11)	0.0230 (10)	0.0186 (9)	0.0006 (8)	−0.0034 (8)	−0.0030 (8)
C4	0.0331 (11)	0.0228 (10)	0.0209 (9)	0.0025 (8)	−0.0042 (8)	0.0008 (8)
C5	0.0273 (10)	0.0192 (9)	0.0222 (9)	−0.0018 (8)	0.0009 (8)	−0.0014 (7)
C6	0.0281 (10)	0.0238 (10)	0.0206 (9)	−0.0016 (8)	−0.0032 (8)	−0.0038 (8)
C7	0.0305 (11)	0.0259 (10)	0.0233 (10)	0.0051 (8)	−0.0066 (8)	−0.0002 (8)
C8	0.0327 (11)	0.0210 (10)	0.0233 (10)	0.0011 (8)	−0.0037 (8)	0.0006 (8)
N9	0.0294 (9)	0.0169 (8)	0.0241 (8)	0.0009 (7)	0.0013 (7)	−0.0004 (6)
N10	0.0284 (9)	0.0173 (8)	0.0214 (8)	0.0009 (7)	−0.0014 (7)	−0.0003 (6)
C11	0.0236 (9)	0.0181 (9)	0.0192 (9)	−0.0019 (7)	0.0024 (7)	0.0033 (7)
N12	0.0271 (9)	0.0180 (8)	0.0207 (8)	0.0014 (7)	−0.0017 (7)	−0.0006 (6)
N13	0.0286 (9)	0.0270 (9)	0.0187 (8)	−0.0004 (7)	−0.0030 (7)	0.0015 (7)
C14	0.0330 (11)	0.0283 (11)	0.0186 (9)	−0.0011 (9)	−0.0025 (8)	−0.0028 (8)
C15	0.0293 (10)	0.0227 (10)	0.0192 (9)	−0.0014 (8)	0.0033 (8)	0.0012 (8)
C16	0.0417 (13)	0.0247 (10)	0.0246 (10)	−0.0009 (9)	0.0049 (9)	−0.0043 (8)
C17	0.0444 (13)	0.0209 (10)	0.0345 (12)	0.0084 (9)	0.0109 (10)	0.0006 (9)
C18	0.0313 (11)	0.0285 (11)	0.0318 (11)	0.0083 (9)	0.0042 (9)	0.0054 (9)
C19	0.0269 (10)	0.0248 (10)	0.0230 (10)	0.0004 (8)	0.0002 (8)	0.0012 (8)
C20	0.0243 (10)	0.0182 (9)	0.0193 (9)	−0.0016 (7)	0.0029 (7)	0.0015 (7)
O21	0.0345 (8)	0.0226 (7)	0.0248 (7)	0.0038 (6)	−0.0060 (6)	−0.0051 (6)
C22	0.0287 (10)	0.0201 (9)	0.0173 (9)	−0.0011 (8)	0.0017 (7)	0.0013 (7)
C23	0.0275 (10)	0.0254 (10)	0.0230 (10)	−0.0047 (8)	−0.0038 (8)	−0.0049 (8)
C24	0.0242 (10)	0.0259 (10)	0.0239 (10)	−0.0009 (8)	−0.0032 (8)	−0.0012 (8)
C25	0.0267 (10)	0.0211 (9)	0.0184 (9)	−0.0024 (8)	0.0011 (7)	0.0013 (7)
C26	0.0298 (11)	0.0239 (10)	0.0219 (9)	−0.0027 (8)	−0.0055 (8)	−0.0036 (8)
C27	0.0253 (10)	0.0261 (10)	0.0236 (10)	0.0015 (8)	−0.0058 (8)	−0.0005 (8)
C28	0.0258 (10)	0.0235 (10)	0.0198 (9)	0.0003 (8)	−0.0014 (7)	0.0016 (8)
N29	0.0298 (9)	0.0190 (8)	0.0211 (8)	0.0026 (7)	−0.0008 (7)	0.0002 (6)
N30	0.0283 (9)	0.0172 (8)	0.0201 (8)	0.0019 (6)	−0.0001 (7)	0.0008 (6)
C31	0.0228 (9)	0.0194 (9)	0.0194 (9)	−0.0017 (7)	0.0013 (7)	0.0038 (7)
N32	0.0264 (9)	0.0197 (8)	0.0200 (8)	0.0022 (7)	−0.0016 (7)	−0.0009 (6)
N33	0.0251 (9)	0.0256 (9)	0.0198 (8)	−0.0010 (7)	−0.0024 (7)	0.0011 (7)
C34	0.0267 (10)	0.0268 (10)	0.0185 (9)	−0.0036 (8)	−0.0009 (8)	−0.0015 (8)
C35	0.0246 (10)	0.0222 (10)	0.0209 (9)	−0.0034 (8)	0.0020 (8)	0.0004 (8)
C36	0.0318 (11)	0.0254 (10)	0.0272 (10)	−0.0024 (8)	0.0030 (8)	−0.0056 (8)
C37	0.0371 (12)	0.0217 (10)	0.0349 (12)	0.0040 (9)	0.0065 (9)	−0.0035 (9)
C38	0.0319 (11)	0.0263 (11)	0.0300 (11)	0.0059 (9)	0.0017 (9)	0.0045 (9)
C39	0.0297 (11)	0.0241 (10)	0.0204 (9)	0.0007 (8)	0.0003 (8)	0.0014 (8)
C40	0.0251 (10)	0.0185 (9)	0.0197 (9)	−0.0020 (7)	0.0037 (7)	0.0025 (7)
C41	0.0405 (14)	0.0379 (14)	0.0551 (16)	0.0013 (11)	−0.0010 (12)	0.0142 (12)
Cl42	0.0683 (5)	0.0620 (5)	0.0621 (5)	0.0183 (4)	−0.0004 (4)	−0.0331 (4)
Cl43	0.0477 (4)	0.0930 (7)	0.0743 (5)	−0.0117 (4)	0.0106 (4)	−0.0558 (5)
C44	0.0432 (15)	0.0532 (17)	0.0474 (15)	0.0103 (12)	−0.0037 (12)	−0.0068 (13)
Cl45	0.0365 (4)	0.0652 (5)	0.0628 (5)	0.0060 (3)	0.0006 (3)	−0.0071 (4)
Cl46	0.0462 (4)	0.0531 (4)	0.0604 (4)	0.0153 (3)	0.0128 (3)	0.0121 (3)

Geometric parameters (Å, º)

O1—C2	1.352 (2)	C23—C24	1.387 (3)
O1—H1	0.8200	C23—H23	0.9300
C2—C3	1.392 (3)	C24—C25	1.393 (3)
C2—C7	1.396 (3)	C24—H24	0.9300
C3—C4	1.383 (3)	C25—C26	1.398 (3)
C3—H3	0.9300	C25—C28	1.459 (3)
C4—C5	1.397 (3)	C26—C27	1.380 (3)
C4—H4	0.9300	C26—H26	0.9300
C5—C6	1.396 (3)	C27—H27	0.9300
C5—C8	1.457 (3)	C28—N29	1.279 (3)
C6—C7	1.381 (3)	C28—H28	0.9300
C6—H6	0.9300	N29—N30	1.403 (2)
C7—H7	0.9300	N30—C31	1.311 (3)
C8—N9	1.278 (3)	C31—N32	1.367 (3)
C8—H8	0.9300	C31—C40	1.461 (3)
N9—N10	1.399 (2)	N32—N33	1.365 (2)
N10—C11	1.314 (3)	N32—H32	0.8600
C11—N12	1.362 (3)	N33—C34	1.288 (3)
C11—C20	1.461 (3)	C34—C35	1.441 (3)
N12—N13	1.366 (2)	C34—H34	0.9300
N12—H12	0.8600	C35—C36	1.398 (3)
N13—C14	1.289 (3)	C35—C40	1.402 (3)
C14—C15	1.442 (3)	C36—C37	1.379 (3)
C14—H14	0.9300	C36—H36	0.9300
C15—C16	1.400 (3)	C37—C38	1.397 (3)
C15—C20	1.401 (3)	C37—H37	0.9300
C16—C17	1.376 (3)	C38—C39	1.377 (3)
C16—H16	0.9300	C38—H38	0.9300
C17—C18	1.398 (3)	C39—C40	1.405 (3)
C17—H17	0.9300	C39—H39	0.9300
C18—C19	1.377 (3)	C41—Cl42	1.738 (3)
C18—H18	0.9300	C41—Cl43	1.767 (3)
C19—C20	1.401 (3)	C41—H41A	0.9700
C19—H19	0.9300	C41—H41B	0.9700
O21—C22	1.358 (2)	C44—Cl46	1.752 (3)
O21—H21	0.8200	C44—Cl45	1.757 (3)
C22—C27	1.393 (3)	C44—H44A	0.9700
C22—C23	1.393 (3)	C44—H44B	0.9700
C2—O1—H1	109.5	C22—C23—H23	120.0
O1—C2—C3	122.65 (18)	C23—C24—C25	121.30 (19)
O1—C2—C7	117.96 (18)	C23—C24—H24	119.4
C3—C2—C7	119.38 (18)	C25—C24—H24	119.4
C4—C3—C2	119.99 (18)	C24—C25—C26	117.98 (19)
C4—C3—H3	120.0	C24—C25—C28	120.61 (18)
C2—C3—H3	120.0	C26—C25—C28	121.37 (18)
C3—C4—C5	121.21 (19)	C27—C26—C25	121.26 (18)
C3—C4—H4	119.4	C27—C26—H26	119.4
C5—C4—H4	119.4	C25—C26—H26	119.4
C6—C5—C4	118.15 (18)	C26—C27—C22	120.16 (19)
C6—C5—C8	122.38 (18)	C26—C27—H27	119.9
C4—C5—C8	119.42 (18)	C22—C27—H27	119.9
C7—C6—C5	121.04 (18)	N29—C28—C25	121.46 (18)
C7—C6—H6	119.5	N29—C28—H28	119.3
C5—C6—H6	119.5	C25—C28—H28	119.3
C6—C7—C2	120.17 (19)	C28—N29—N30	114.02 (17)
C6—C7—H7	119.9	C31—N30—N29	111.35 (16)
C2—C7—H7	119.9	N30—C31—N32	122.65 (18)
N9—C8—C5	122.13 (19)	N30—C31—C40	121.41 (17)
N9—C8—H8	118.9	N32—C31—C40	115.94 (17)
C5—C8—H8	118.9	N33—N32—C31	126.97 (17)
C8—N9—N10	112.70 (17)	N33—N32—H32	116.5
C11—N10—N9	112.09 (16)	C31—N32—H32	116.5
N10—C11—N12	123.19 (18)	C34—N33—N32	116.68 (17)
N10—C11—C20	120.52 (17)	N33—C34—C35	124.31 (18)
N12—C11—C20	116.29 (17)	N33—C34—H34	117.8
C11—N12—N13	126.69 (17)	C35—C34—H34	117.8
C11—N12—H12	116.7	C36—C35—C40	120.33 (19)
N13—N12—H12	116.7	C36—C35—C34	121.43 (18)
C14—N13—N12	116.60 (17)	C40—C35—C34	118.22 (18)
N13—C14—C15	124.62 (19)	C37—C36—C35	119.91 (19)
N13—C14—H14	117.7	C37—C36—H36	120.0
C15—C14—H14	117.7	C35—C36—H36	120.0
C16—C15—C20	119.74 (19)	C36—C37—C38	119.8 (2)
C16—C15—C14	122.42 (19)	C36—C37—H37	120.1
C20—C15—C14	117.84 (18)	C38—C37—H37	120.1
C17—C16—C15	120.1 (2)	C39—C38—C37	121.0 (2)
C17—C16—H16	119.9	C39—C38—H38	119.5
C15—C16—H16	119.9	C37—C38—H38	119.5
C16—C17—C18	120.1 (2)	C38—C39—C40	119.80 (19)
C16—C17—H17	120.0	C38—C39—H39	120.1
C18—C17—H17	120.0	C40—C39—H39	120.1
C19—C18—C17	120.6 (2)	C35—C40—C39	119.11 (18)
C19—C18—H18	119.7	C35—C40—C31	117.83 (17)
C17—C18—H18	119.7	C39—C40—C31	123.06 (18)
C18—C19—C20	119.86 (19)	Cl42—C41—Cl43	110.30 (15)
C18—C19—H19	120.1	Cl42—C41—H41A	109.6
C20—C19—H19	120.1	Cl43—C41—H41A	109.6
C15—C20—C19	119.60 (18)	Cl42—C41—H41B	109.6
C15—C20—C11	117.90 (17)	Cl43—C41—H41B	109.6
C19—C20—C11	122.50 (18)	H41A—C41—H41B	108.1
C22—O21—H21	109.5	Cl46—C44—Cl45	111.33 (16)
O21—C22—C27	118.02 (18)	Cl46—C44—H44A	109.4
O21—C22—C23	122.63 (18)	Cl45—C44—H44A	109.4
C27—C22—C23	119.34 (19)	Cl46—C44—H44B	109.4
C24—C23—C22	119.94 (18)	Cl45—C44—H44B	109.4
C24—C23—H23	120.0	H44A—C44—H44B	108.0
O1—C2—C3—C4	178.1 (2)	O21—C22—C23—C24	−179.07 (19)
C7—C2—C3—C4	−1.7 (3)	C27—C22—C23—C24	1.1 (3)
C2—C3—C4—C5	−0.6 (3)	C22—C23—C24—C25	−0.4 (3)
C3—C4—C5—C6	2.1 (3)	C23—C24—C25—C26	−0.3 (3)
C3—C4—C5—C8	179.6 (2)	C23—C24—C25—C28	177.22 (19)
C4—C5—C6—C7	−1.4 (3)	C24—C25—C26—C27	0.3 (3)
C8—C5—C6—C7	−178.8 (2)	C28—C25—C26—C27	−177.20 (19)
C5—C6—C7—C2	−0.9 (3)	C25—C26—C27—C22	0.4 (3)
O1—C2—C7—C6	−177.4 (2)	O21—C22—C27—C26	179.07 (18)
C3—C2—C7—C6	2.4 (3)	C23—C22—C27—C26	−1.1 (3)
C6—C5—C8—N9	−12.7 (3)	C24—C25—C28—N29	178.5 (2)
C4—C5—C8—N9	170.0 (2)	C26—C25—C28—N29	−4.0 (3)
C5—C8—N9—N10	178.55 (18)	C25—C28—N29—N30	178.85 (17)
C8—N9—N10—C11	−177.10 (18)	C28—N29—N30—C31	164.67 (18)
N9—N10—C11—N12	−3.8 (3)	N29—N30—C31—N32	0.8 (3)
N9—N10—C11—C20	176.29 (16)	N29—N30—C31—C40	−178.71 (16)
N10—C11—N12—N13	−177.53 (19)	N30—C31—N32—N33	−177.83 (18)
C20—C11—N12—N13	2.4 (3)	C40—C31—N32—N33	1.7 (3)
C11—N12—N13—C14	−0.4 (3)	C31—N32—N33—C34	0.4 (3)
N12—N13—C14—C15	−1.1 (3)	N32—N33—C34—C35	−1.7 (3)
N13—C14—C15—C16	−179.2 (2)	N33—C34—C35—C36	−177.4 (2)
N13—C14—C15—C20	0.5 (3)	N33—C34—C35—C40	0.7 (3)
C20—C15—C16—C17	−1.7 (3)	C40—C35—C36—C37	−1.2 (3)
C14—C15—C16—C17	177.9 (2)	C34—C35—C36—C37	176.9 (2)
C15—C16—C17—C18	0.4 (3)	C35—C36—C37—C38	1.7 (3)
C16—C17—C18—C19	0.6 (3)	C36—C37—C38—C39	−0.2 (3)
C17—C18—C19—C20	−0.2 (3)	C37—C38—C39—C40	−1.7 (3)
C16—C15—C20—C19	2.1 (3)	C36—C35—C40—C39	−0.7 (3)
C14—C15—C20—C19	−177.58 (19)	C34—C35—C40—C39	−178.90 (18)
C16—C15—C20—C11	−178.78 (18)	C36—C35—C40—C31	179.64 (18)
C14—C15—C20—C11	1.6 (3)	C34—C35—C40—C31	1.5 (3)
C18—C19—C20—C15	−1.1 (3)	C38—C39—C40—C35	2.2 (3)
C18—C19—C20—C11	179.80 (19)	C38—C39—C40—C31	−178.23 (19)
N10—C11—C20—C15	177.07 (18)	N30—C31—C40—C35	177.02 (18)
N12—C11—C20—C15	−2.8 (3)	N32—C31—C40—C35	−2.5 (3)
N10—C11—C20—C19	−3.8 (3)	N30—C31—C40—C39	−2.6 (3)
N12—C11—C20—C19	176.30 (18)	N32—C31—C40—C39	177.84 (18)

(IsBr)

Crystal data

C13H10BrN3O	F(000) = 608
Mr = 304.15	Dx = 1.640 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.763 (3) Å	Cell parameters from 2623 reflections
b = 6.5126 (7) Å	θ = 3.3–25.3°
c = 10.1237 (15) Å	µ = 3.33 mm^−1
β = 95.458 (15)°	T = 297 K
V = 1231.5 (3) Å^3	Hexagonal plate, colourless
Z = 4	0.18 × 0.18 × 0.03 mm

Data collection

MAR345 image plate diffractometer	2245 independent reflections
Radiation source: Rigaku UltraX 18 rotating anode	1785 reflections with I > 2σ(I)
Xenocs Fox3D mirror monochromator	Rint = 0.059
80 images, ΔΦ 2.5° scans	θmax = 25.4°, θmin = 3.3°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −22→22
Tmin = 0.533, Tmax = 1.000	k = −7→7
8113 measured reflections	l = −11→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0587P)^2 + 0.7961P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2245 reflections	Δρmax = 0.43 e Å^−3
163 parameters	Δρmin = −0.57 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
Br1	0.96154 (3)	1.35783 (6)	0.64628 (6)	0.0835 (3)
C2	0.8979 (2)	1.1317 (5)	0.6458 (4)	0.0499 (9)
C3	0.8525 (2)	1.1150 (5)	0.7442 (4)	0.0524 (9)
H3	0.8518	1.2160	0.8090	0.063*
C4	0.8083 (2)	0.9469 (5)	0.7452 (3)	0.0471 (8)
H4	0.7769	0.9358	0.8107	0.057*
C5	0.80968 (18)	0.7925 (5)	0.6498 (3)	0.0416 (7)
C6	0.85567 (19)	0.8164 (5)	0.5503 (3)	0.0458 (8)
H6	0.8567	0.7164	0.4849	0.055*
C7	0.89904 (19)	0.9840 (6)	0.5473 (3)	0.0516 (8)
H7	0.9291	0.9991	0.4800	0.062*
C8	0.76359 (19)	0.6140 (5)	0.6590 (3)	0.0436 (8)
H8	0.7433	0.5908	0.7380	0.052*
N9	0.74983 (15)	0.4875 (4)	0.5631 (2)	0.0402 (6)
N10	0.70509 (16)	0.3288 (4)	0.5908 (2)	0.0418 (6)
H10	0.6924	0.3153	0.6698	0.050*
C11	0.68097 (18)	0.1944 (5)	0.4955 (3)	0.0393 (7)
O12	0.69702 (15)	0.2019 (4)	0.3812 (2)	0.0560 (7)
C13	0.63082 (16)	0.0330 (5)	0.5387 (3)	0.0361 (7)
C14	0.58709 (19)	0.0629 (6)	0.6394 (3)	0.0477 (8)
H14	0.5890	0.1853	0.6868	0.057*
C15	0.5405 (2)	−0.0915 (6)	0.6688 (4)	0.0573 (10)
H15	0.5104	−0.0673	0.7351	0.069*
N16	0.53605 (18)	−0.2731 (5)	0.6075 (3)	0.0567 (8)
C17	0.5786 (2)	−0.3005 (6)	0.5116 (4)	0.0553 (9)
H17	0.5767	−0.4261	0.4677	0.066*
C18	0.6255 (2)	−0.1536 (5)	0.4730 (3)	0.0472 (8)
H18	0.6532	−0.1799	0.4035	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0776 (4)	0.0490 (3)	0.1235 (5)	−0.0193 (2)	0.0078 (3)	−0.0001 (2)
C2	0.049 (2)	0.0384 (18)	0.061 (2)	−0.0016 (15)	−0.0038 (17)	0.0053 (15)
C3	0.065 (3)	0.0421 (19)	0.050 (2)	0.0059 (17)	0.0011 (17)	−0.0072 (15)
C4	0.054 (2)	0.0489 (19)	0.0391 (17)	0.0042 (16)	0.0100 (14)	−0.0018 (15)
C5	0.047 (2)	0.0429 (17)	0.0347 (16)	0.0022 (14)	0.0023 (13)	0.0030 (13)
C6	0.050 (2)	0.0478 (18)	0.0403 (17)	0.0003 (15)	0.0084 (15)	−0.0053 (14)
C7	0.047 (2)	0.056 (2)	0.0534 (19)	−0.0061 (17)	0.0125 (16)	0.0038 (17)
C8	0.050 (2)	0.0449 (18)	0.0370 (17)	−0.0014 (15)	0.0113 (14)	0.0023 (14)
N9	0.0448 (16)	0.0395 (14)	0.0369 (13)	−0.0019 (12)	0.0070 (11)	0.0045 (12)
N10	0.0531 (18)	0.0448 (15)	0.0289 (13)	−0.0056 (13)	0.0103 (11)	0.0032 (11)
C11	0.0448 (19)	0.0411 (16)	0.0324 (16)	0.0067 (14)	0.0065 (13)	0.0027 (13)
O12	0.0762 (19)	0.0633 (15)	0.0307 (12)	−0.0109 (14)	0.0173 (11)	−0.0034 (11)
C13	0.0374 (17)	0.0395 (16)	0.0310 (14)	0.0026 (13)	0.0015 (12)	0.0025 (12)
C14	0.052 (2)	0.0504 (19)	0.0416 (17)	−0.0064 (16)	0.0097 (15)	−0.0069 (15)
C15	0.057 (2)	0.072 (2)	0.0449 (19)	−0.013 (2)	0.0171 (17)	−0.0015 (18)
N16	0.061 (2)	0.0584 (19)	0.0513 (17)	−0.0138 (17)	0.0055 (15)	0.0065 (15)
C17	0.062 (3)	0.0433 (18)	0.059 (2)	−0.0016 (17)	−0.0033 (18)	−0.0007 (17)
C18	0.051 (2)	0.0463 (19)	0.0450 (18)	0.0027 (15)	0.0081 (15)	−0.0047 (14)

Geometric parameters (Å, º)

Br1—C2	1.895 (3)	N10—C11	1.349 (4)
C2—C3	1.375 (6)	N10—H10	0.8600
C2—C7	1.387 (5)	C11—O12	1.224 (4)
C3—C4	1.375 (5)	C11—C13	1.503 (4)
C3—H3	0.9300	C13—C14	1.381 (4)
C4—C5	1.396 (5)	C13—C18	1.385 (4)
C4—H4	0.9300	C14—C15	1.384 (5)
C5—C6	1.397 (5)	C14—H14	0.9300
C5—C8	1.457 (5)	C15—N16	1.334 (5)
C6—C7	1.363 (5)	C15—H15	0.9300
C6—H6	0.9300	N16—C17	1.326 (5)
C7—H7	0.9300	C17—C18	1.382 (5)
C8—N9	1.280 (4)	C17—H17	0.9300
C8—H8	0.9300	C18—H18	0.9300
N9—N10	1.377 (4)
C3—C2—C7	121.2 (3)	C11—N10—N9	120.7 (2)
C3—C2—Br1	119.6 (3)	C11—N10—H10	119.6
C7—C2—Br1	119.2 (3)	N9—N10—H10	119.6
C2—C3—C4	119.0 (3)	O12—C11—N10	123.7 (3)
C2—C3—H3	120.5	O12—C11—C13	121.4 (3)
C4—C3—H3	120.5	N10—C11—C13	115.0 (2)
C3—C4—C5	121.1 (3)	C14—C13—C18	117.2 (3)
C3—C4—H4	119.4	C14—C13—C11	123.3 (3)
C5—C4—H4	119.4	C18—C13—C11	119.5 (3)
C4—C5—C6	118.2 (3)	C13—C14—C15	119.3 (3)
C4—C5—C8	118.7 (3)	C13—C14—H14	120.4
C6—C5—C8	123.1 (3)	C15—C14—H14	120.4
C7—C6—C5	121.1 (3)	N16—C15—C14	123.8 (3)
C7—C6—H6	119.5	N16—C15—H15	118.1
C5—C6—H6	119.5	C14—C15—H15	118.1
C6—C7—C2	119.3 (3)	C17—N16—C15	116.4 (3)
C6—C7—H7	120.3	N16—C17—C18	123.9 (3)
C2—C7—H7	120.3	N16—C17—H17	118.1
N9—C8—C5	122.9 (3)	C18—C17—H17	118.1
N9—C8—H8	118.5	C17—C18—C13	119.4 (3)
C5—C8—H8	118.5	C17—C18—H18	120.3
C8—N9—N10	114.3 (3)	C13—C18—H18	120.3
C7—C2—C3—C4	0.9 (6)	N9—N10—C11—O12	0.7 (5)
Br1—C2—C3—C4	−177.9 (3)	N9—N10—C11—C13	−178.2 (3)
C2—C3—C4—C5	1.0 (5)	O12—C11—C13—C14	−150.8 (3)
C3—C4—C5—C6	−2.0 (5)	N10—C11—C13—C14	28.2 (4)
C3—C4—C5—C8	177.6 (3)	O12—C11—C13—C18	27.0 (5)
C4—C5—C6—C7	1.1 (5)	N10—C11—C13—C18	−154.1 (3)
C8—C5—C6—C7	−178.5 (3)	C18—C13—C14—C15	−0.4 (5)
C5—C6—C7—C2	0.7 (5)	C11—C13—C14—C15	177.3 (3)
C3—C2—C7—C6	−1.8 (6)	C13—C14—C15—N16	1.8 (6)
Br1—C2—C7—C6	177.0 (3)	C14—C15—N16—C17	−1.4 (6)
C4—C5—C8—N9	164.9 (3)	C15—N16—C17—C18	−0.3 (6)
C6—C5—C8—N9	−15.4 (5)	N16—C17—C18—C13	1.6 (6)
C5—C8—N9—N10	−179.9 (3)	C14—C13—C18—C17	−1.1 (5)
C8—N9—N10—C11	174.1 (3)	C11—C13—C18—C17	−179.0 (3)