4-(4-Bromo­phen­yl)-3-meth­yl-1-phen­yl-4,5-dihydro-1H-pyrazolo[3,4-b]pyridin-6(7H)-one

The title compound, C₁₉H₁₆BrN₃O, was synthesized by the reaction of 5-amino-3-meth­yl-1-phenyl­pyrazole with 4-bromo­phenyl­aldehyde and Medrum's acid in glycol under microwave irradiation. X-ray crystal structure analysis reveals three crystallographically independent mol­ecules in the asymmetric unit. In all these mol­ecules, the dihydro­pyridine ring adopts a distorted envelope conformation. In the crystal structure, the mol­ecules exist as N—H...O hydrogen-bonded dimers.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.079
• wR factor = 0.157
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.88(6), Rep   0.881(10) ......       6.00 su-Rat
              N4   -H4      1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.88(6), Rep   0.880(10) ......       6.00 su-Rat
              N4   -H4      1.555   1.555

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    Br3    -   C54     ..       6.05 su
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT731_ALERT_1_C Bond    Calc     0.89(3), Rep   0.883(10) ......       3.00 su-Rat
              N1   -H1      1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.88(4), Rep   0.877(10) ......       4.00 su-Rat
              N7   -H7      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.89(3), Rep   0.880(10) ......       3.00 su-Rat
              N1   -H1      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.88(4), Rep   0.880(10) ......       4.00 su-Rat
              N7   -H7      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.93(4), Rep   1.940(10) ......       4.00 su-Rat
              H1   -O1      1.555   3.766
PLAT736_ALERT_1_C H...A   Calc     1.94(5), Rep     1.94(2) ......       2.50 su-Rat
              H4   -O3      1.555   4.575
PLAT736_ALERT_1_C H...A   Calc     1.96(4), Rep   1.960(10) ......       4.00 su-Rat
              H7   -O2      1.555   4.576

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

   9 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
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

4-(4-Bromophenyl)-3-methyl-1-phenyl-4,5-dihydro-1H-pyrazolo[3,4-b]pyridine- 6(7H)-one

Crystal data

C19H16BrN3O	F(000) = 2328
Mr = 382.26	Dx = 1.515 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 19389 reflections
a = 13.905 (2) Å	θ = 3.0–25.3°
b = 17.965 (3) Å	µ = 2.46 mm^−1
c = 20.505 (4) Å	T = 193 K
β = 101.026 (7)°	Block, colourless
V = 5027.5 (15) Å^3	0.60 × 0.40 × 0.39 mm
Z = 12

Data collection

Rigaku Mercury CCD area-detector diffractometer	9180 independent reflections
Radiation source: fine-focus sealed tube	7942 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 7.31 pixels mm^-1	θmax = 25.4°, θmin = 3.0°
ω scans	h = −16→16
Absorption correction: multi-scan (Jacobson, 1998)	k = −20→21
Tmin = 0.274, Tmax = 0.383	l = −24→24
48280 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0145P)^2 + 35.9447P] where P = (Fo^2 + 2Fc^2)/3
9180 reflections	(Δ/σ)max = 0.001
665 parameters	Δρmax = 1.91 e Å^−3
3 restraints	Δρmin = −0.98 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	1.06779 (6)	0.63714 (4)	0.01764 (3)	0.0472 (2)
Br2	0.57949 (6)	0.37851 (4)	0.62983 (4)	0.0537 (2)
Br3	0.77044 (7)	0.85290 (4)	0.17049 (4)	0.0604 (2)
O1	1.0878 (3)	0.4738 (2)	0.4544 (2)	0.0418 (11)
O2	0.5680 (3)	0.5191 (2)	0.1881 (2)	0.0412 (11)
O3	0.7373 (3)	1.0364 (2)	0.5937 (2)	0.0396 (10)
N1	0.9619 (4)	0.5535 (3)	0.4211 (2)	0.0317 (11)
N2	0.7820 (4)	0.6559 (3)	0.3073 (2)	0.0342 (12)
N3	0.8284 (3)	0.6368 (3)	0.3705 (2)	0.0299 (11)
N4	0.6955 (4)	0.4417 (3)	0.2212 (2)	0.0312 (11)
N5	0.8713 (4)	0.3327 (3)	0.3331 (2)	0.0334 (11)
N6	0.8250 (3)	0.3544 (3)	0.2699 (2)	0.0290 (10)
N7	0.6141 (4)	0.9547 (3)	0.5612 (2)	0.0293 (11)
N8	0.4608 (3)	0.8266 (3)	0.4542 (2)	0.0298 (11)
N9	0.4943 (3)	0.8596 (3)	0.5147 (2)	0.0271 (10)
C1	0.9025 (4)	0.5881 (3)	0.3670 (3)	0.0285 (12)
C2	0.9060 (4)	0.5754 (3)	0.3029 (3)	0.0305 (13)
C3	0.9813 (5)	0.5241 (3)	0.2842 (3)	0.0350 (14)
H3	0.9526	0.4729	0.2776	0.042*
C4	1.0680 (5)	0.5223 (4)	0.3436 (3)	0.0388 (15)
H4A	1.1122	0.4809	0.3369	0.047*
H4B	1.1054	0.5692	0.3439	0.047*
C5	1.0402 (4)	0.5129 (3)	0.4099 (3)	0.0351 (14)
C6	0.8288 (4)	0.6195 (3)	0.2664 (3)	0.0337 (13)
C7	0.8014 (4)	0.6729 (3)	0.4249 (3)	0.0311 (13)
C8	0.8707 (5)	0.6979 (4)	0.4773 (3)	0.0405 (15)
H8	0.9383	0.6899	0.4776	0.049*
C9	0.8422 (6)	0.7348 (4)	0.5294 (3)	0.0502 (18)
H9	0.8902	0.7517	0.5658	0.060*
C10	0.7448 (6)	0.7471 (4)	0.5289 (4)	0.055 (2)
H10	0.7251	0.7733	0.5644	0.067*
C11	0.6761 (5)	0.7215 (4)	0.4768 (4)	0.051 (2)
H11	0.6087	0.7299	0.4768	0.062*
C12	0.7021 (5)	0.6843 (3)	0.4252 (4)	0.0406 (16)
H12	0.6534	0.6663	0.3897	0.049*
C13	1.0123 (5)	0.5480 (3)	0.2209 (3)	0.0345 (14)
C14	1.0491 (5)	0.6190 (3)	0.2154 (3)	0.0366 (14)
H14	1.0619	0.6503	0.2535	0.044*
C15	1.0675 (5)	0.6453 (3)	0.1554 (3)	0.0372 (14)
H15	1.0926	0.6940	0.1521	0.045*
C16	1.0488 (5)	0.6000 (3)	0.1010 (3)	0.0348 (14)
C17	1.0153 (6)	0.5280 (4)	0.1050 (3)	0.0509 (19)
H17	1.0055	0.4963	0.0672	0.061*
C18	0.9965 (6)	0.5033 (4)	0.1649 (3)	0.0491 (18)
H18	0.9721	0.4543	0.1678	0.059*
C19	0.7974 (5)	0.6289 (4)	0.1937 (3)	0.0448 (16)
H19A	0.7375	0.6589	0.1845	0.067*
H19B	0.7847	0.5800	0.1727	0.067*
H19C	0.8492	0.6541	0.1758	0.067*
C20	0.7534 (4)	0.4040 (3)	0.2745 (3)	0.0262 (12)
C21	0.7499 (4)	0.4156 (3)	0.3397 (3)	0.0308 (13)
C22	0.6783 (4)	0.4698 (3)	0.3588 (3)	0.0331 (13)
H22	0.7107	0.5197	0.3646	0.040*
C23	0.5915 (4)	0.4750 (4)	0.3002 (3)	0.0370 (15)
H23A	0.5504	0.4300	0.3004	0.044*
H23B	0.5511	0.5185	0.3074	0.044*
C24	0.6179 (4)	0.4820 (3)	0.2325 (3)	0.0325 (13)
C25	0.8253 (4)	0.3698 (3)	0.3737 (3)	0.0308 (13)
C26	0.8521 (4)	0.3189 (3)	0.2145 (3)	0.0292 (13)
C27	0.9505 (5)	0.3041 (3)	0.2159 (3)	0.0362 (14)
H27	0.9992	0.3200	0.2522	0.043*
C28	0.9759 (5)	0.2655 (4)	0.1631 (3)	0.0421 (16)
H28	1.0429	0.2547	0.1634	0.050*
C29	0.9053 (5)	0.2424 (4)	0.1101 (3)	0.0444 (17)
H29	0.9237	0.2152	0.0747	0.053*
C30	0.8086 (5)	0.2589 (4)	0.1086 (3)	0.0447 (17)
H30	0.7601	0.2437	0.0719	0.054*
C31	0.7820 (5)	0.2977 (4)	0.1607 (3)	0.0383 (15)
H31	0.7151	0.3098	0.1594	0.046*
C32	0.6474 (4)	0.4495 (3)	0.4238 (3)	0.0308 (13)
C33	0.6677 (5)	0.4960 (3)	0.4782 (3)	0.0411 (16)
H33	0.6971	0.5430	0.4737	0.049*
C34	0.6467 (5)	0.4764 (4)	0.5387 (3)	0.0467 (17)
H34	0.6614	0.5095	0.5754	0.056*
C35	0.6044 (5)	0.4087 (3)	0.5457 (3)	0.0376 (14)
C36	0.5820 (5)	0.3608 (3)	0.4925 (3)	0.0416 (16)
H36	0.5523	0.3140	0.4972	0.050*
C37	0.6034 (5)	0.3822 (3)	0.4325 (3)	0.0437 (16)
H37	0.5873	0.3495	0.3956	0.052*
C38	0.8567 (5)	0.3578 (4)	0.4465 (3)	0.0468 (17)
H38A	0.9138	0.3247	0.4547	0.070*
H38B	0.8030	0.3351	0.4642	0.070*
H38C	0.8740	0.4057	0.4684	0.070*
C39	0.5653 (4)	0.9099 (3)	0.5096 (3)	0.0273 (12)
C40	0.5797 (4)	0.9114 (3)	0.4461 (3)	0.0269 (12)
C41	0.6508 (4)	0.9660 (3)	0.4273 (3)	0.0314 (13)
H41	0.6159	1.0145	0.4166	0.038*
C42	0.7324 (4)	0.9779 (3)	0.4882 (3)	0.0346 (14)
H42A	0.7744	0.9330	0.4947	0.042*
H42B	0.7736	1.0202	0.4794	0.042*
C43	0.6951 (4)	0.9932 (3)	0.5516 (3)	0.0317 (13)
C44	0.5136 (4)	0.8575 (3)	0.4138 (3)	0.0297 (12)
C45	0.4559 (4)	0.8357 (3)	0.5713 (3)	0.0306 (13)
C46	0.3566 (4)	0.8283 (3)	0.5663 (3)	0.0353 (14)
H46	0.3134	0.8395	0.5257	0.042*
C47	0.3193 (5)	0.8042 (4)	0.6214 (4)	0.0479 (18)
H47	0.2507	0.7979	0.6179	0.057*
C48	0.3811 (7)	0.7899 (4)	0.6799 (4)	0.058 (2)
H48	0.3555	0.7749	0.7176	0.069*
C49	0.4811 (6)	0.7970 (4)	0.6845 (4)	0.056 (2)
H49	0.5241	0.7858	0.7252	0.067*
C50	0.5192 (5)	0.8203 (4)	0.6300 (3)	0.0469 (17)
H50	0.5879	0.8254	0.6332	0.056*
C51	0.6914 (4)	0.9419 (3)	0.3668 (3)	0.0294 (13)
C52	0.6759 (5)	0.9857 (3)	0.3108 (3)	0.0398 (15)
H52	0.6471	1.0335	0.3119	0.048*
C53	0.7023 (5)	0.9603 (4)	0.2523 (3)	0.0439 (16)
H53	0.6921	0.9905	0.2136	0.053*
C54	0.7434 (5)	0.8904 (3)	0.2520 (3)	0.0346 (14)
C55	0.7628 (5)	0.8475 (3)	0.3074 (3)	0.0389 (15)
H55	0.7940	0.8005	0.3067	0.047*
C56	0.7360 (4)	0.8737 (3)	0.3654 (3)	0.0341 (14)
H56	0.7487	0.8441	0.4045	0.041*
C57	0.5021 (5)	0.8293 (4)	0.3442 (3)	0.0390 (15)
H57A	0.5579	0.7974	0.3404	0.058*
H57B	0.4995	0.8715	0.3136	0.058*
H57C	0.4413	0.8005	0.3330	0.058*
H1	0.945 (4)	0.549 (3)	0.4604 (13)	0.025 (15)*
H4	0.714 (6)	0.448 (5)	0.183 (2)	0.07 (3)*
H7	0.597 (4)	0.961 (3)	0.5998 (14)	0.029 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0667 (5)	0.0405 (4)	0.0384 (4)	0.0011 (3)	0.0204 (3)	−0.0002 (3)
Br2	0.0833 (6)	0.0431 (4)	0.0402 (4)	−0.0016 (4)	0.0255 (4)	−0.0011 (3)
Br3	0.1005 (6)	0.0459 (4)	0.0433 (4)	−0.0090 (4)	0.0349 (4)	−0.0081 (3)
O1	0.047 (3)	0.043 (3)	0.037 (2)	0.019 (2)	0.012 (2)	0.011 (2)
O2	0.046 (3)	0.040 (2)	0.040 (3)	0.021 (2)	0.015 (2)	0.012 (2)
O3	0.049 (3)	0.036 (2)	0.036 (2)	−0.018 (2)	0.013 (2)	−0.013 (2)
N1	0.038 (3)	0.031 (3)	0.028 (3)	0.009 (2)	0.013 (2)	0.009 (2)
N2	0.034 (3)	0.030 (3)	0.037 (3)	0.000 (2)	0.001 (2)	0.006 (2)
N3	0.032 (3)	0.027 (2)	0.033 (3)	0.002 (2)	0.009 (2)	0.003 (2)
N4	0.038 (3)	0.030 (3)	0.028 (3)	0.012 (2)	0.012 (2)	0.009 (2)
N5	0.038 (3)	0.023 (2)	0.038 (3)	0.006 (2)	0.003 (2)	−0.001 (2)
N6	0.034 (3)	0.027 (2)	0.027 (3)	0.007 (2)	0.007 (2)	0.002 (2)
N7	0.037 (3)	0.028 (3)	0.025 (3)	−0.007 (2)	0.012 (2)	−0.006 (2)
N8	0.030 (3)	0.028 (3)	0.032 (3)	−0.003 (2)	0.008 (2)	−0.005 (2)
N9	0.029 (2)	0.026 (2)	0.029 (3)	−0.005 (2)	0.014 (2)	−0.004 (2)
C1	0.027 (3)	0.025 (3)	0.035 (3)	0.001 (2)	0.011 (2)	0.004 (2)
C2	0.038 (3)	0.022 (3)	0.032 (3)	0.001 (2)	0.007 (3)	0.004 (2)
C3	0.046 (4)	0.024 (3)	0.039 (3)	−0.003 (3)	0.016 (3)	−0.001 (3)
C4	0.045 (4)	0.041 (4)	0.036 (3)	0.013 (3)	0.020 (3)	0.007 (3)
C5	0.037 (3)	0.031 (3)	0.039 (4)	0.005 (3)	0.012 (3)	0.004 (3)
C6	0.035 (3)	0.028 (3)	0.037 (3)	−0.005 (3)	0.004 (3)	0.001 (3)
C7	0.035 (3)	0.021 (3)	0.041 (3)	0.001 (2)	0.015 (3)	0.010 (2)
C8	0.033 (3)	0.044 (4)	0.048 (4)	0.003 (3)	0.017 (3)	−0.001 (3)
C9	0.058 (5)	0.058 (5)	0.038 (4)	0.007 (4)	0.019 (3)	−0.001 (3)
C10	0.072 (5)	0.053 (5)	0.050 (5)	0.026 (4)	0.034 (4)	0.019 (4)
C11	0.049 (4)	0.047 (4)	0.069 (5)	0.022 (3)	0.037 (4)	0.029 (4)
C12	0.031 (3)	0.033 (3)	0.060 (4)	0.006 (3)	0.015 (3)	0.015 (3)
C13	0.041 (3)	0.029 (3)	0.035 (3)	0.000 (3)	0.012 (3)	0.005 (3)
C14	0.044 (4)	0.030 (3)	0.038 (3)	−0.006 (3)	0.014 (3)	−0.006 (3)
C15	0.047 (4)	0.023 (3)	0.043 (4)	−0.006 (3)	0.015 (3)	0.001 (3)
C16	0.045 (4)	0.025 (3)	0.038 (3)	−0.002 (3)	0.016 (3)	0.000 (3)
C17	0.090 (6)	0.033 (4)	0.033 (4)	−0.007 (4)	0.020 (4)	−0.009 (3)
C18	0.076 (5)	0.028 (3)	0.044 (4)	−0.011 (3)	0.014 (4)	−0.008 (3)
C19	0.047 (4)	0.051 (4)	0.033 (4)	0.002 (3)	−0.002 (3)	0.004 (3)
C20	0.028 (3)	0.019 (3)	0.032 (3)	0.003 (2)	0.008 (2)	0.000 (2)
C21	0.030 (3)	0.020 (3)	0.043 (4)	0.000 (2)	0.009 (3)	−0.001 (3)
C22	0.041 (3)	0.025 (3)	0.035 (3)	0.002 (3)	0.012 (3)	0.002 (3)
C23	0.039 (3)	0.041 (4)	0.035 (3)	0.015 (3)	0.018 (3)	0.002 (3)
C24	0.036 (3)	0.029 (3)	0.034 (3)	0.005 (3)	0.012 (3)	0.005 (3)
C25	0.033 (3)	0.027 (3)	0.031 (3)	0.001 (2)	0.002 (2)	−0.001 (2)
C26	0.034 (3)	0.024 (3)	0.035 (3)	0.007 (2)	0.020 (3)	0.007 (2)
C27	0.038 (3)	0.029 (3)	0.044 (4)	0.005 (3)	0.013 (3)	0.005 (3)
C28	0.038 (4)	0.041 (4)	0.054 (4)	0.015 (3)	0.029 (3)	0.001 (3)
C29	0.059 (4)	0.045 (4)	0.033 (4)	0.016 (3)	0.018 (3)	0.002 (3)
C30	0.055 (4)	0.052 (4)	0.028 (3)	0.014 (3)	0.010 (3)	−0.003 (3)
C31	0.039 (4)	0.045 (4)	0.031 (3)	0.012 (3)	0.007 (3)	−0.003 (3)
C32	0.036 (3)	0.023 (3)	0.033 (3)	0.002 (2)	0.007 (3)	−0.003 (2)
C33	0.062 (4)	0.024 (3)	0.038 (4)	−0.009 (3)	0.012 (3)	−0.001 (3)
C34	0.072 (5)	0.028 (3)	0.040 (4)	−0.010 (3)	0.012 (3)	−0.008 (3)
C35	0.050 (4)	0.032 (3)	0.033 (3)	0.003 (3)	0.013 (3)	0.000 (3)
C36	0.051 (4)	0.025 (3)	0.052 (4)	−0.009 (3)	0.018 (3)	−0.012 (3)
C37	0.064 (5)	0.027 (3)	0.043 (4)	−0.008 (3)	0.018 (3)	−0.015 (3)
C38	0.057 (4)	0.045 (4)	0.033 (4)	0.011 (3)	−0.005 (3)	−0.003 (3)
C39	0.033 (3)	0.017 (3)	0.032 (3)	−0.002 (2)	0.006 (2)	0.001 (2)
C40	0.031 (3)	0.024 (3)	0.026 (3)	0.004 (2)	0.007 (2)	0.000 (2)
C41	0.038 (3)	0.024 (3)	0.035 (3)	0.003 (2)	0.012 (3)	−0.001 (2)
C42	0.036 (3)	0.038 (3)	0.034 (3)	−0.011 (3)	0.017 (3)	−0.007 (3)
C43	0.036 (3)	0.023 (3)	0.040 (3)	−0.003 (2)	0.014 (3)	−0.002 (3)
C44	0.029 (3)	0.027 (3)	0.032 (3)	0.003 (2)	0.003 (2)	−0.001 (2)
C45	0.035 (3)	0.020 (3)	0.037 (3)	−0.005 (2)	0.009 (3)	−0.005 (2)
C46	0.030 (3)	0.030 (3)	0.051 (4)	−0.001 (3)	0.019 (3)	−0.003 (3)
C47	0.048 (4)	0.035 (4)	0.068 (5)	−0.005 (3)	0.030 (4)	−0.008 (3)
C48	0.091 (6)	0.040 (4)	0.052 (5)	−0.015 (4)	0.037 (4)	−0.010 (4)
C49	0.071 (5)	0.047 (4)	0.047 (4)	−0.021 (4)	0.004 (4)	0.006 (3)
C50	0.054 (4)	0.038 (4)	0.047 (4)	−0.017 (3)	0.006 (3)	0.001 (3)
C51	0.034 (3)	0.024 (3)	0.031 (3)	−0.003 (2)	0.009 (2)	0.000 (2)
C52	0.054 (4)	0.025 (3)	0.043 (4)	0.003 (3)	0.016 (3)	0.006 (3)
C53	0.068 (5)	0.034 (3)	0.033 (3)	0.003 (3)	0.019 (3)	0.011 (3)
C54	0.053 (4)	0.036 (3)	0.021 (3)	−0.005 (3)	0.022 (3)	−0.010 (3)
C55	0.051 (4)	0.025 (3)	0.043 (4)	0.005 (3)	0.016 (3)	0.001 (3)
C56	0.043 (4)	0.030 (3)	0.032 (3)	0.002 (3)	0.015 (3)	0.011 (3)
C57	0.041 (4)	0.041 (4)	0.034 (3)	−0.006 (3)	0.005 (3)	−0.004 (3)

Geometric parameters (Å, º)

Br1—C16	1.899 (6)	C22—C23	1.534 (8)
Br2—C35	1.902 (6)	C22—H22	1.00
Br3—C54	1.904 (5)	C23—C24	1.509 (8)
O1—C5	1.238 (7)	C23—H23A	0.99
O2—C24	1.229 (7)	C23—H23B	0.99
O3—C43	1.224 (7)	C25—C38	1.487 (8)
N1—C5	1.365 (7)	C26—C31	1.378 (8)
N1—C1	1.396 (7)	C26—C27	1.388 (8)
N1—H1	0.883 (10)	C27—C28	1.387 (9)
N2—C6	1.329 (8)	C27—H27	0.95
N2—N3	1.375 (7)	C28—C29	1.381 (10)
N3—C1	1.365 (7)	C28—H28	0.95
N3—C7	1.403 (7)	C29—C30	1.371 (9)
N4—C24	1.355 (7)	C29—H29	0.95
N4—C20	1.401 (7)	C30—C31	1.384 (8)
N4—H4	0.881 (10)	C30—H30	0.95
N5—C25	1.324 (7)	C31—H31	0.95
N5—N6	1.388 (7)	C32—C33	1.379 (8)
N6—C20	1.352 (7)	C32—C37	1.382 (8)
N6—C26	1.417 (7)	C33—C34	1.374 (9)
N7—C43	1.368 (7)	C33—H33	0.95
N7—C39	1.398 (7)	C34—C35	1.371 (9)
N7—H7	0.877 (10)	C34—H34	0.95
N8—C44	1.330 (7)	C35—C36	1.377 (8)
N8—N9	1.373 (6)	C36—C37	1.375 (9)
N9—C39	1.357 (7)	C36—H36	0.95
N9—C45	1.433 (7)	C37—H37	0.95
C1—C2	1.343 (8)	C38—H38A	0.98
C2—C6	1.426 (8)	C38—H38B	0.98
C2—C3	1.500 (8)	C38—H38C	0.98
C3—C13	1.506 (8)	C39—C40	1.357 (8)
C3—C4	1.542 (9)	C40—C44	1.409 (8)
C3—H3	1.00	C40—C41	1.495 (8)
C4—C5	1.492 (8)	C41—C51	1.520 (8)
C4—H4A	0.99	C41—C42	1.533 (8)
C4—H4B	0.99	C41—H41	1.00
C6—C19	1.480 (8)	C42—C43	1.513 (8)
C7—C8	1.374 (9)	C42—H42A	0.99
C7—C12	1.398 (8)	C42—H42B	0.99
C8—C9	1.378 (9)	C44—C57	1.493 (8)
C8—H8	0.95	C45—C46	1.371 (8)
C9—C10	1.370 (10)	C45—C50	1.376 (9)
C9—H9	0.95	C46—C47	1.398 (9)
C10—C11	1.370 (11)	C46—H46	0.95
C10—H10	0.95	C47—C48	1.360 (11)
C11—C12	1.358 (10)	C47—H47	0.95
C11—H11	0.95	C48—C49	1.381 (11)
C12—H12	0.95	C48—H48	0.95
C13—C18	1.384 (9)	C49—C50	1.391 (10)
C13—C14	1.388 (8)	C49—H49	0.95
C14—C15	1.387 (8)	C50—H50	0.95
C14—H14	0.95	C51—C52	1.374 (8)
C15—C16	1.365 (8)	C51—C56	1.376 (8)
C15—H15	0.95	C52—C53	1.395 (9)
C16—C17	1.382 (9)	C52—H52	0.95
C17—C18	1.378 (9)	C53—C54	1.381 (9)
C17—H17	0.95	C53—H53	0.95
C18—H18	0.95	C54—C55	1.357 (8)
C19—H19A	0.98	C55—C56	1.395 (8)
C19—H19B	0.98	C55—H55	0.95
C19—H19C	0.98	C56—H56	0.95
C20—C21	1.365 (8)	C57—H57A	0.98
C21—C25	1.408 (8)	C57—H57B	0.98
C21—C22	1.498 (8)	C57—H57C	0.98
C22—C32	1.520 (8)
C5—N1—C1	118.3 (5)	C21—C25—C38	129.0 (6)
C5—N1—H1	118 (4)	C31—C26—C27	120.5 (6)
C1—N1—H1	123 (4)	C31—C26—N6	120.7 (5)
C6—N2—N3	105.9 (5)	C27—C26—N6	118.8 (6)
C1—N3—N2	109.5 (5)	C28—C27—C26	118.5 (6)
C1—N3—C7	131.1 (5)	C28—C27—H27	120.8
N2—N3—C7	119.1 (5)	C26—C27—H27	120.8
C24—N4—C20	119.0 (5)	C29—C28—C27	121.0 (6)
C24—N4—H4	118 (5)	C29—C28—H28	119.5
C20—N4—H4	122 (5)	C27—C28—H28	119.5
C25—N5—N6	104.6 (4)	C30—C29—C28	120.0 (6)
C20—N6—N5	109.7 (4)	C30—C29—H29	120.0
C20—N6—C26	131.6 (5)	C28—C29—H29	120.0
N5—N6—C26	118.4 (4)	C29—C30—C31	119.9 (6)
C43—N7—C39	118.4 (5)	C29—C30—H30	120.1
C43—N7—H7	117 (4)	C31—C30—H30	120.1
C39—N7—H7	125 (4)	C26—C31—C30	120.2 (6)
C44—N8—N9	104.5 (4)	C26—C31—H31	119.9
C39—N9—N8	110.2 (4)	C30—C31—H31	119.9
C39—N9—C45	130.6 (5)	C33—C32—C37	116.9 (6)
N8—N9—C45	119.2 (4)	C33—C32—C22	121.0 (5)
C2—C1—N3	109.2 (5)	C37—C32—C22	121.9 (5)
C2—C1—N1	125.1 (5)	C34—C33—C32	122.0 (6)
N3—C1—N1	125.6 (5)	C34—C33—H33	119.0
C1—C2—C6	104.8 (5)	C32—C33—H33	119.0
C1—C2—C3	120.8 (5)	C35—C34—C33	119.5 (6)
C6—C2—C3	134.4 (6)	C35—C34—H34	120.3
C2—C3—C13	112.0 (5)	C33—C34—H34	120.3
C2—C3—C4	106.8 (5)	C34—C35—C36	120.5 (6)
C13—C3—C4	112.2 (5)	C34—C35—Br2	120.3 (5)
C2—C3—H3	108.6	C36—C35—Br2	119.2 (5)
C13—C3—H3	108.6	C37—C36—C35	118.7 (6)
C4—C3—H3	108.6	C37—C36—H36	120.7
C5—C4—C3	115.0 (5)	C35—C36—H36	120.7
C5—C4—H4A	108.5	C36—C37—C32	122.5 (6)
C3—C4—H4A	108.5	C36—C37—H37	118.8
C5—C4—H4B	108.5	C32—C37—H37	118.8
C3—C4—H4B	108.5	C25—C38—H38A	109.5
H4A—C4—H4B	107.5	C25—C38—H38B	109.5
O1—C5—N1	120.6 (5)	H38A—C38—H38B	109.5
O1—C5—C4	122.7 (5)	C25—C38—H38C	109.5
N1—C5—C4	116.6 (5)	H38A—C38—H38C	109.5
N2—C6—C2	110.6 (5)	H38B—C38—H38C	109.5
N2—C6—C19	119.6 (6)	C40—C39—N9	109.3 (5)
C2—C6—C19	129.8 (6)	C40—C39—N7	125.2 (5)
C8—C7—C12	119.7 (6)	N9—C39—N7	125.5 (5)
C8—C7—N3	121.3 (5)	C39—C40—C44	103.6 (5)
C12—C7—N3	119.1 (6)	C39—C40—C41	119.1 (5)
C7—C8—C9	120.0 (6)	C44—C40—C41	137.2 (5)
C7—C8—H8	120.0	C40—C41—C51	112.9 (5)
C9—C8—H8	120.0	C40—C41—C42	107.7 (5)
C10—C9—C8	120.2 (7)	C51—C41—C42	111.8 (5)
C10—C9—H9	119.9	C40—C41—H41	108.1
C8—C9—H9	119.9	C51—C41—H41	108.1
C11—C10—C9	119.5 (7)	C42—C41—H41	108.1
C11—C10—H10	120.3	C43—C42—C41	113.8 (5)
C9—C10—H10	120.3	C43—C42—H42A	108.8
C12—C11—C10	121.6 (7)	C41—C42—H42A	108.8
C12—C11—H11	119.2	C43—C42—H42B	108.8
C10—C11—H11	119.2	C41—C42—H42B	108.8
C11—C12—C7	119.0 (7)	H42A—C42—H42B	107.7
C11—C12—H12	120.5	O3—C43—N7	121.0 (5)
C7—C12—H12	120.5	O3—C43—C42	121.6 (5)
C18—C13—C14	117.9 (6)	N7—C43—C42	117.4 (5)
C18—C13—C3	121.6 (6)	N8—C44—C40	112.5 (5)
C14—C13—C3	120.2 (5)	N8—C44—C57	118.8 (5)
C15—C14—C13	121.2 (6)	C40—C44—C57	128.5 (5)
C15—C14—H14	119.4	C46—C45—C50	120.8 (6)
C13—C14—H14	119.4	C46—C45—N9	119.6 (5)
C16—C15—C14	119.0 (6)	C50—C45—N9	119.5 (5)
C16—C15—H15	120.5	C45—C46—C47	119.6 (6)
C14—C15—H15	120.5	C45—C46—H46	120.2
C15—C16—C17	121.5 (6)	C47—C46—H46	120.2
C15—C16—Br1	119.2 (4)	C48—C47—C46	120.1 (7)
C17—C16—Br1	119.3 (5)	C48—C47—H47	120.0
C18—C17—C16	118.6 (6)	C46—C47—H47	120.0
C18—C17—H17	120.7	C47—C48—C49	120.1 (7)
C16—C17—H17	120.7	C47—C48—H48	120.0
C17—C18—C13	121.7 (6)	C49—C48—H48	120.0
C17—C18—H18	119.1	C48—C49—C50	120.4 (7)
C13—C18—H18	119.1	C48—C49—H49	119.8
C6—C19—H19A	109.5	C50—C49—H49	119.8
C6—C19—H19B	109.5	C45—C50—C49	119.0 (7)
H19A—C19—H19B	109.5	C45—C50—H50	120.5
C6—C19—H19C	109.5	C49—C50—H50	120.5
H19A—C19—H19C	109.5	C52—C51—C56	119.4 (5)
H19B—C19—H19C	109.5	C52—C51—C41	119.7 (5)
N6—C20—C21	109.5 (5)	C56—C51—C41	120.7 (5)
N6—C20—N4	125.9 (5)	C51—C52—C53	120.4 (6)
C21—C20—N4	124.5 (5)	C51—C52—H52	119.8
C20—C21—C25	103.5 (5)	C53—C52—H52	119.8
C20—C21—C22	120.4 (5)	C54—C53—C52	118.6 (6)
C25—C21—C22	136.0 (6)	C54—C53—H53	120.7
C21—C22—C32	112.8 (5)	C52—C53—H53	120.7
C21—C22—C23	107.3 (5)	C55—C54—C53	121.9 (5)
C32—C22—C23	112.9 (5)	C55—C54—Br3	119.5 (5)
C21—C22—H22	107.9	C53—C54—Br3	118.6 (5)
C32—C22—H22	107.9	C54—C55—C56	118.6 (6)
C23—C22—H22	107.9	C54—C55—H55	120.7
C24—C23—C22	115.7 (5)	C56—C55—H55	120.7
C24—C23—H23A	108.4	C51—C56—C55	120.9 (5)
C22—C23—H23A	108.4	C51—C56—H56	119.5
C24—C23—H23B	108.4	C55—C56—H56	119.5
C22—C23—H23B	108.4	C44—C57—H57A	109.5
H23A—C23—H23B	107.4	C44—C57—H57B	109.5
O2—C24—N4	121.2 (5)	H57A—C57—H57B	109.5
O2—C24—C23	121.7 (5)	C44—C57—H57C	109.5
N4—C24—C23	116.9 (5)	H57A—C57—H57C	109.5
N5—C25—C21	112.7 (5)	H57B—C57—H57C	109.5
N5—C25—C38	118.3 (5)
C6—N2—N3—C1	−0.7 (6)	C22—C21—C25—N5	−177.7 (6)
C6—N2—N3—C7	173.5 (5)	C20—C21—C25—C38	−179.3 (6)
C25—N5—N6—C20	0.4 (6)	C22—C21—C25—C38	3.3 (11)
C25—N5—N6—C26	−174.4 (5)	C20—N6—C26—C31	−36.1 (9)
C44—N8—N9—C39	0.7 (6)	N5—N6—C26—C31	137.4 (6)
C44—N8—N9—C45	−176.7 (5)	C20—N6—C26—C27	145.6 (6)
N2—N3—C1—C2	0.5 (6)	N5—N6—C26—C27	−40.9 (7)
C7—N3—C1—C2	−172.8 (5)	C31—C26—C27—C28	−2.0 (9)
N2—N3—C1—N1	−176.2 (5)	N6—C26—C27—C28	176.3 (5)
C7—N3—C1—N1	10.5 (9)	C26—C27—C28—C29	0.2 (9)
C5—N1—C1—C2	11.4 (9)	C27—C28—C29—C30	1.3 (10)
C5—N1—C1—N3	−172.5 (5)	C28—C29—C30—C31	−0.9 (10)
N3—C1—C2—C6	0.0 (6)	C27—C26—C31—C30	2.4 (9)
N1—C1—C2—C6	176.7 (5)	N6—C26—C31—C30	−175.9 (6)
N3—C1—C2—C3	179.5 (5)	C29—C30—C31—C26	−0.9 (10)
N1—C1—C2—C3	−3.8 (9)	C21—C22—C32—C33	117.3 (6)
C1—C2—C3—C13	−147.5 (6)	C23—C22—C32—C33	−120.9 (6)
C6—C2—C3—C13	31.9 (9)	C21—C22—C32—C37	−58.7 (8)
C1—C2—C3—C4	−24.4 (7)	C23—C22—C32—C37	63.1 (8)
C6—C2—C3—C4	155.0 (6)	C37—C32—C33—C34	0.9 (10)
C2—C3—C4—C5	46.1 (7)	C22—C32—C33—C34	−175.3 (6)
C13—C3—C4—C5	169.2 (5)	C32—C33—C34—C35	0.1 (11)
C1—N1—C5—O1	−171.0 (6)	C33—C34—C35—C36	−0.7 (11)
C1—N1—C5—C4	12.7 (8)	C33—C34—C35—Br2	177.4 (5)
C3—C4—C5—O1	141.0 (6)	C34—C35—C36—C37	0.3 (10)
C3—C4—C5—N1	−42.8 (8)	Br2—C35—C36—C37	−177.8 (5)
N3—N2—C6—C2	0.7 (6)	C35—C36—C37—C32	0.7 (11)
N3—N2—C6—C19	−179.1 (5)	C33—C32—C37—C36	−1.3 (10)
C1—C2—C6—N2	−0.5 (7)	C22—C32—C37—C36	174.9 (6)
C3—C2—C6—N2	−179.9 (6)	N8—N9—C39—C40	0.2 (6)
C1—C2—C6—C19	179.4 (6)	C45—N9—C39—C40	177.2 (5)
C3—C2—C6—C19	−0.1 (11)	N8—N9—C39—N7	178.6 (5)
C1—N3—C7—C8	37.1 (9)	C45—N9—C39—N7	−4.4 (9)
N2—N3—C7—C8	−135.7 (6)	C43—N7—C39—C40	−13.0 (8)
C1—N3—C7—C12	−143.9 (6)	C43—N7—C39—N9	168.8 (5)
N2—N3—C7—C12	43.4 (7)	N9—C39—C40—C44	−1.0 (6)
C12—C7—C8—C9	−0.6 (9)	N7—C39—C40—C44	−179.4 (5)
N3—C7—C8—C9	178.4 (6)	N9—C39—C40—C41	176.5 (5)
C7—C8—C9—C10	−0.6 (11)	N7—C39—C40—C41	−1.9 (9)
C8—C9—C10—C11	1.1 (11)	C39—C40—C41—C51	156.0 (5)
C9—C10—C11—C12	−0.4 (11)	C44—C40—C41—C51	−27.6 (9)
C10—C11—C12—C7	−0.8 (10)	C39—C40—C41—C42	32.0 (7)
C8—C7—C12—C11	1.3 (9)	C44—C40—C41—C42	−151.6 (7)
N3—C7—C12—C11	−177.7 (5)	C40—C41—C42—C43	−48.6 (6)
C2—C3—C13—C18	−117.5 (7)	C51—C41—C42—C43	−173.3 (5)
C4—C3—C13—C18	122.4 (7)	C39—N7—C43—O3	175.9 (5)
C2—C3—C13—C14	56.1 (8)	C39—N7—C43—C42	−6.4 (8)
C4—C3—C13—C14	−64.0 (7)	C41—C42—C43—O3	−144.1 (6)
C18—C13—C14—C15	1.4 (10)	C41—C42—C43—N7	38.2 (8)
C3—C13—C14—C15	−172.5 (6)	N9—N8—C44—C40	−1.3 (6)
C13—C14—C15—C16	0.0 (10)	N9—N8—C44—C57	174.8 (5)
C14—C15—C16—C17	−2.2 (10)	C39—C40—C44—N8	1.5 (6)
C14—C15—C16—Br1	177.0 (5)	C41—C40—C44—N8	−175.3 (6)
C15—C16—C17—C18	2.9 (11)	C39—C40—C44—C57	−174.1 (6)
Br1—C16—C17—C18	−176.3 (6)	C41—C40—C44—C57	9.1 (11)
C16—C17—C18—C13	−1.4 (12)	C39—N9—C45—C46	135.9 (6)
C14—C13—C18—C17	−0.7 (11)	N8—N9—C45—C46	−47.4 (7)
C3—C13—C18—C17	173.1 (7)	C39—N9—C45—C50	−44.4 (9)
N5—N6—C20—C21	−0.6 (6)	N8—N9—C45—C50	132.3 (6)
C26—N6—C20—C21	173.3 (5)	C50—C45—C46—C47	−0.5 (9)
N5—N6—C20—N4	175.6 (5)	N9—C45—C46—C47	179.3 (5)
C26—N6—C20—N4	−10.5 (10)	C45—C46—C47—C48	1.4 (10)
C24—N4—C20—N6	171.2 (5)	C46—C47—C48—C49	−1.9 (11)
C24—N4—C20—C21	−13.2 (9)	C47—C48—C49—C50	1.3 (11)
N6—C20—C21—C25	0.5 (6)	C46—C45—C50—C49	−0.1 (10)
N4—C20—C21—C25	−175.7 (5)	N9—C45—C50—C49	−179.8 (6)
N6—C20—C21—C22	178.5 (5)	C48—C49—C50—C45	−0.4 (11)
N4—C20—C21—C22	2.2 (9)	C40—C41—C51—C52	119.4 (6)
C20—C21—C22—C32	151.1 (5)	C42—C41—C51—C52	−118.9 (6)
C25—C21—C22—C32	−31.7 (9)	C40—C41—C51—C56	−54.9 (8)
C20—C21—C22—C23	26.2 (7)	C42—C41—C51—C56	66.7 (7)
C25—C21—C22—C23	−156.7 (7)	C56—C51—C52—C53	2.1 (10)
C21—C22—C23—C24	−45.2 (7)	C41—C51—C52—C53	−172.3 (6)
C32—C22—C23—C24	−170.1 (5)	C51—C52—C53—C54	0.4 (10)
C20—N4—C24—O2	176.2 (5)	C52—C53—C54—C55	−3.1 (10)
C20—N4—C24—C23	−8.0 (8)	C52—C53—C54—Br3	175.5 (5)
C22—C23—C24—O2	−145.6 (6)	C53—C54—C55—C56	3.1 (10)
C22—C23—C24—N4	38.6 (8)	Br3—C54—C55—C56	−175.4 (5)
N6—N5—C25—C21	−0.1 (6)	C52—C51—C56—C55	−2.1 (9)
N6—N5—C25—C38	179.0 (5)	C41—C51—C56—C55	172.3 (6)
C20—C21—C25—N5	−0.2 (7)	C54—C55—C56—C51	−0.4 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88 (1)	1.94 (1)	2.812 (6)	172 (5)
N4—H4···O3^ii	0.88 (1)	1.94 (2)	2.814 (6)	173 (8)
N7—H7···O2^iii	0.88 (1)	1.96 (1)	2.834 (6)	174 (6)
C4—H4A···Br3^iv	0.99	2.84	3.826 (7)	173

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+2, y−1/2, −z+1/2.