6,9-Dibromo-2a,10b-diphenyl-2a,5,10,10b-tetra­hydro-2H,3H-2,3,4a,10a-tetra­azabenzo[g]cyclo­penta­[cd]azulene-1,4-dione monohydrate

The title compound, C₂₄H₁₈Br₂N₄O₂·H₂O, forms a supra­molecular structure via N—H...O, O—H...O and C—H...O hydrogen bonds. In the crystal structure, the water molecule serves as a bifurcated hydrogen-bond acceptor and as a hydrogen-bond donor.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.053
• wR factor = 0.136
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.91
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.46 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C23
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         11

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.914
            Tmax scaled      0.488 Tmin scaled      0.377

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

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

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

6,9-Dibromo-2a,10b-diphenyl-2a,5,10,10b-tetrahydro-2H,3H-2,3,4a, 10a-tetraaza-benzo[g]cyclopenta[cd]azulene-1,4-dione hydrate

Crystal data

C24H18Br2N4O2·H2O	F(000) = 1144
Mr = 572.26	Dx = 1.666 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3096 reflections
a = 13.066 (2) Å	θ = 2.3–21.7°
b = 9.9260 (15) Å	µ = 3.59 mm^−1
c = 18.351 (3) Å	T = 292 K
β = 106.539 (3)°	Prism, colorless
V = 2281.5 (6) Å^3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART 4K CCD area-detector diffractometer	5151 independent reflections
Radiation source: fine-focus sealed tube	3218 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick 1997)	h = −13→16
Tmin = 0.412, Tmax = 0.534	k = −12→12
14118 measured reflections	l = −23→23

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0625P)^2] where P = (Fo^2 + 2Fc^2)/3
5151 reflections	(Δ/σ)max < 0.001
306 parameters	Δρmax = 0.68 e Å^−3
51 restraints	Δρmin = −0.56 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	0.11556 (7)	0.73670 (9)	0.39639 (5)	0.0716 (4)
Br2	−0.03296 (7)	0.10457 (10)	0.37718 (5)	0.0776 (4)
C1	0.1132 (5)	0.4707 (7)	0.4607 (3)	0.0365 (15)
C2	0.0761 (5)	0.5518 (8)	0.3963 (4)	0.0484 (18)
C3	0.0064 (6)	0.5019 (10)	0.3297 (4)	0.061 (2)
H3	−0.0190	0.5582	0.2880	0.073*
C4	−0.0246 (6)	0.3701 (10)	0.3258 (4)	0.062 (2)
H4	−0.0710	0.3361	0.2813	0.075*
C5	0.0135 (5)	0.2873 (8)	0.3883 (4)	0.0485 (18)
C6	0.0829 (4)	0.3355 (7)	0.4559 (3)	0.0369 (15)
C7	0.1197 (5)	0.2437 (6)	0.5247 (4)	0.0363 (14)
H7A	0.0893	0.2759	0.5640	0.044*
H7B	0.0919	0.1539	0.5104	0.044*
C8	0.1812 (4)	0.5298 (6)	0.5352 (3)	0.0347 (14)
H8A	0.1915	0.6250	0.5277	0.042*
H8B	0.1421	0.5221	0.5727	0.042*
C9	0.2955 (5)	0.1307 (6)	0.5429 (3)	0.0346 (14)
C10	0.3638 (5)	0.4824 (6)	0.5300 (3)	0.0340 (14)
C11	0.2964 (4)	0.3401 (6)	0.6051 (3)	0.0283 (12)
C12	0.2688 (4)	0.3493 (6)	0.6797 (3)	0.0321 (13)
C13	0.2240 (5)	0.2414 (7)	0.7077 (4)	0.0437 (16)
H13	0.2035	0.1646	0.6781	0.052*
C14	0.2096 (6)	0.2479 (9)	0.7798 (4)	0.060 (2)
H14	0.1810	0.1746	0.7989	0.072*
C15	0.2371 (6)	0.3603 (10)	0.8222 (4)	0.069 (2)
H15	0.2269	0.3635	0.8703	0.083*
C16	0.2797 (6)	0.4699 (9)	0.7961 (4)	0.063 (2)
H16	0.2979	0.5468	0.8260	0.075*
C17	0.2954 (5)	0.4647 (7)	0.7231 (4)	0.0450 (16)
H17	0.3236	0.5386	0.7043	0.054*
C18	0.4156 (4)	0.2943 (6)	0.6099 (3)	0.0314 (13)
C19	0.4986 (5)	0.3037 (7)	0.6861 (4)	0.0382 (15)
C20	0.4872 (6)	0.2300 (8)	0.7464 (4)	0.058 (2)
H20	0.4310	0.1693	0.7393	0.069*
C21	0.5589 (8)	0.2451 (10)	0.8182 (5)	0.074 (3)
H21	0.5476	0.1987	0.8593	0.089*
C22	0.6447 (9)	0.3264 (10)	0.8289 (5)	0.087 (3)
H22	0.6928	0.3358	0.8769	0.104*
C23	0.6598 (8)	0.3942 (10)	0.7687 (6)	0.098 (4)
H23	0.7205	0.4471	0.7753	0.118*
C24	0.5863 (6)	0.3859 (8)	0.6972 (5)	0.065 (2)
H24	0.5964	0.4360	0.6570	0.078*
N1	0.2351 (4)	0.2352 (5)	0.5563 (3)	0.0314 (11)
N2	0.2860 (4)	0.4671 (5)	0.5661 (3)	0.0302 (11)
N3	0.3992 (4)	0.1563 (5)	0.5825 (3)	0.0368 (12)
H3C	0.4493	0.0972	0.5904	0.044*
N4	0.4358 (4)	0.3848 (5)	0.5532 (3)	0.0381 (13)
H4A	0.4902	0.3760	0.5359	0.046*
O1	0.2612 (3)	0.0326 (4)	0.5041 (2)	0.0448 (11)
O2	0.3659 (3)	0.5750 (4)	0.4854 (3)	0.0448 (11)
O3	0.4032 (4)	0.8572 (6)	0.4646 (4)	0.0690 (14)
H3B	0.362 (4)	0.919 (4)	0.476 (3)	0.0500 (18)*
H3A	0.380 (5)	0.779 (3)	0.472 (4)	0.0500 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0554 (5)	0.0762 (6)	0.0875 (7)	0.0164 (4)	0.0272 (5)	0.0447 (5)
Br2	0.0617 (6)	0.0907 (7)	0.0696 (6)	−0.0180 (5)	0.0013 (4)	−0.0267 (5)
C1	0.028 (3)	0.051 (4)	0.037 (3)	0.010 (3)	0.019 (3)	0.005 (3)
C2	0.037 (4)	0.069 (5)	0.046 (4)	0.019 (3)	0.022 (3)	0.018 (4)
C3	0.048 (4)	0.100 (7)	0.037 (4)	0.026 (4)	0.016 (3)	0.015 (4)
C4	0.042 (4)	0.102 (7)	0.037 (4)	0.021 (4)	0.002 (3)	−0.009 (4)
C5	0.031 (4)	0.070 (5)	0.043 (4)	0.009 (3)	0.010 (3)	−0.009 (4)
C6	0.023 (3)	0.055 (4)	0.035 (3)	0.010 (3)	0.012 (3)	−0.002 (3)
C7	0.027 (3)	0.041 (4)	0.042 (3)	−0.004 (3)	0.011 (3)	−0.003 (3)
C8	0.029 (3)	0.039 (4)	0.040 (3)	0.010 (3)	0.015 (3)	0.008 (3)
C9	0.043 (4)	0.036 (4)	0.028 (3)	0.007 (3)	0.014 (3)	0.006 (3)
C10	0.030 (3)	0.038 (4)	0.036 (3)	0.000 (3)	0.013 (3)	0.001 (3)
C11	0.023 (3)	0.030 (3)	0.033 (3)	0.000 (2)	0.010 (2)	0.002 (2)
C12	0.025 (3)	0.043 (4)	0.029 (3)	0.006 (3)	0.009 (2)	0.004 (3)
C13	0.040 (4)	0.052 (4)	0.041 (4)	0.001 (3)	0.015 (3)	0.006 (3)
C14	0.057 (5)	0.083 (6)	0.048 (4)	−0.005 (4)	0.028 (4)	0.019 (4)
C15	0.059 (5)	0.116 (7)	0.038 (4)	0.001 (5)	0.025 (4)	0.006 (5)
C16	0.061 (5)	0.087 (6)	0.040 (4)	0.001 (4)	0.014 (4)	−0.019 (4)
C17	0.043 (4)	0.053 (4)	0.041 (4)	0.000 (3)	0.014 (3)	−0.001 (3)
C18	0.027 (3)	0.036 (3)	0.036 (3)	0.005 (2)	0.016 (3)	0.005 (3)
C19	0.030 (3)	0.043 (4)	0.040 (4)	0.009 (3)	0.007 (3)	0.000 (3)
C20	0.039 (4)	0.083 (6)	0.049 (4)	0.011 (4)	0.009 (3)	0.022 (4)
C21	0.079 (6)	0.097 (7)	0.044 (4)	0.039 (5)	0.014 (4)	0.015 (4)
C22	0.107 (8)	0.070 (6)	0.057 (5)	0.026 (6)	−0.019 (5)	−0.019 (5)
C23	0.081 (6)	0.070 (6)	0.105 (7)	−0.019 (5)	−0.037 (6)	−0.005 (6)
C24	0.059 (5)	0.056 (5)	0.065 (5)	−0.008 (4)	−0.006 (4)	0.003 (4)
N1	0.027 (3)	0.035 (3)	0.033 (3)	0.002 (2)	0.009 (2)	−0.001 (2)
N2	0.024 (2)	0.035 (3)	0.035 (3)	0.005 (2)	0.014 (2)	0.005 (2)
N3	0.030 (3)	0.035 (3)	0.045 (3)	0.010 (2)	0.009 (2)	0.001 (2)
N4	0.030 (3)	0.047 (3)	0.044 (3)	0.010 (2)	0.021 (2)	0.015 (2)
O1	0.048 (3)	0.040 (3)	0.046 (3)	0.005 (2)	0.012 (2)	−0.010 (2)
O2	0.042 (3)	0.046 (3)	0.054 (3)	0.008 (2)	0.026 (2)	0.022 (2)
O3	0.0637 (17)	0.0547 (18)	0.1056 (18)	0.0114 (11)	0.0516 (13)	0.0077 (11)

Geometric parameters (Å, º)

Br1—C2	1.906 (8)	C12—C13	1.387 (9)
Br2—C5	1.905 (8)	C13—C14	1.391 (10)
C1—C6	1.395 (9)	C13—H13	0.9300
C1—C2	1.397 (8)	C14—C15	1.349 (11)
C1—C8	1.521 (8)	C14—H14	0.9300
C2—C3	1.391 (10)	C15—C16	1.369 (11)
C3—C4	1.366 (11)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.413 (9)
C4—C5	1.384 (10)	C16—H16	0.9300
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.396 (9)	C18—N3	1.453 (8)
C6—C7	1.520 (9)	C18—N4	1.456 (7)
C7—N1	1.455 (7)	C18—C19	1.509 (8)
C7—H7A	0.9700	C19—C20	1.371 (10)
C7—H7B	0.9700	C19—C24	1.373 (10)
C8—N2	1.463 (7)	C20—C21	1.390 (11)
C8—H8A	0.9700	C20—H20	0.9300
C8—H8B	0.9700	C21—C22	1.350 (13)
C9—O1	1.214 (7)	C21—H21	0.9300
C9—N3	1.367 (8)	C22—C23	1.355 (14)
C9—N1	1.368 (7)	C22—H22	0.9300
C10—O2	1.236 (7)	C23—C24	1.390 (12)
C10—N4	1.333 (7)	C23—H23	0.9300
C10—N2	1.371 (7)	C24—H24	0.9300
C11—N2	1.437 (7)	N3—H3C	0.8600
C11—N1	1.455 (7)	N4—H4A	0.8600
C11—C12	1.515 (8)	O3—H3B	0.88 (5)
C11—C18	1.600 (7)	O3—H3A	0.86 (4)
C12—C17	1.382 (9)
C6—C1—C2	118.5 (6)	C15—C14—H14	120.0
C6—C1—C8	120.7 (5)	C13—C14—H14	120.0
C2—C1—C8	120.7 (6)	C14—C15—C16	121.6 (7)
C3—C2—C1	121.3 (7)	C14—C15—H15	119.2
C3—C2—Br1	116.9 (6)	C16—C15—H15	119.2
C1—C2—Br1	121.7 (5)	C15—C16—C17	119.1 (7)
C4—C3—C2	119.9 (7)	C15—C16—H16	120.5
C4—C3—H3	120.0	C17—C16—H16	120.5
C2—C3—H3	120.0	C12—C17—C16	119.7 (7)
C3—C4—C5	119.5 (7)	C12—C17—H17	120.1
C3—C4—H4	120.2	C16—C17—H17	120.1
C5—C4—H4	120.2	N3—C18—N4	111.9 (5)
C4—C5—C6	121.5 (7)	N3—C18—C19	112.0 (5)
C4—C5—Br2	116.6 (6)	N4—C18—C19	113.3 (5)
C6—C5—Br2	121.9 (5)	N3—C18—C11	101.7 (4)
C1—C6—C5	119.1 (6)	N4—C18—C11	99.0 (4)
C1—C6—C7	120.5 (5)	C19—C18—C11	117.8 (4)
C5—C6—C7	120.3 (6)	C20—C19—C24	118.4 (7)
N1—C7—C6	114.4 (5)	C20—C19—C18	120.0 (6)
N1—C7—H7A	108.7	C24—C19—C18	121.6 (6)
C6—C7—H7A	108.7	C19—C20—C21	120.6 (8)
N1—C7—H7B	108.7	C19—C20—H20	119.7
C6—C7—H7B	108.7	C21—C20—H20	119.7
H7A—C7—H7B	107.6	C22—C21—C20	120.6 (9)
N2—C8—C1	115.3 (5)	C22—C21—H21	119.7
N2—C8—H8A	108.5	C20—C21—H21	119.7
C1—C8—H8A	108.5	C21—C22—C23	119.1 (8)
N2—C8—H8B	108.5	C21—C22—H22	120.4
C1—C8—H8B	108.5	C23—C22—H22	120.4
H8A—C8—H8B	107.5	C22—C23—C24	121.2 (9)
O1—C9—N3	127.3 (6)	C22—C23—H23	119.4
O1—C9—N1	125.3 (6)	C24—C23—H23	119.4
N3—C9—N1	107.4 (5)	C19—C24—C23	119.9 (9)
O2—C10—N4	127.2 (5)	C19—C24—H24	120.0
O2—C10—N2	124.2 (5)	C23—C24—H24	120.0
N4—C10—N2	108.6 (5)	C9—N1—C7	123.9 (5)
N2—C11—N1	111.4 (4)	C9—N1—C11	114.1 (5)
N2—C11—C12	112.6 (5)	C7—N1—C11	122.0 (4)
N1—C11—C12	111.6 (5)	C10—N2—C11	111.1 (4)
N2—C11—C18	103.3 (4)	C10—N2—C8	120.5 (5)
N1—C11—C18	100.8 (4)	C11—N2—C8	120.7 (4)
C12—C11—C18	116.4 (4)	C9—N3—C18	112.6 (5)
C17—C12—C13	119.4 (6)	C9—N3—H3C	123.7
C17—C12—C11	119.0 (5)	C18—N3—H3C	123.7
C13—C12—C11	121.5 (6)	C10—N4—C18	114.9 (5)
C12—C13—C14	120.2 (7)	C10—N4—H4A	122.5
C12—C13—H13	119.9	C18—N4—H4A	122.5
C14—C13—H13	119.9	H3B—O3—H3A	109 (4)
C15—C14—C13	120.0 (7)
C6—C1—C2—C3	3.0 (9)	C11—C18—C19—C20	61.6 (8)
C8—C1—C2—C3	−174.4 (5)	N3—C18—C19—C24	124.7 (7)
C6—C1—C2—Br1	−178.5 (4)	N4—C18—C19—C24	−3.1 (8)
C8—C1—C2—Br1	4.0 (7)	C11—C18—C19—C24	−117.9 (7)
C1—C2—C3—C4	−1.9 (10)	C24—C19—C20—C21	4.2 (11)
Br1—C2—C3—C4	179.7 (5)	C18—C19—C20—C21	−175.3 (6)
C2—C3—C4—C5	0.2 (10)	C19—C20—C21—C22	−4.1 (13)
C3—C4—C5—C6	0.2 (10)	C20—C21—C22—C23	0.5 (14)
C3—C4—C5—Br2	−179.4 (5)	C21—C22—C23—C24	2.9 (15)
C2—C1—C6—C5	−2.6 (8)	C20—C19—C24—C23	−0.9 (12)
C8—C1—C6—C5	174.9 (5)	C18—C19—C24—C23	178.6 (7)
C2—C1—C6—C7	−179.0 (5)	C22—C23—C24—C19	−2.7 (15)
C8—C1—C6—C7	−1.5 (8)	O1—C9—N1—C7	−0.8 (9)
C4—C5—C6—C1	1.0 (9)	N3—C9—N1—C7	−179.1 (5)
Br2—C5—C6—C1	−179.4 (4)	O1—C9—N1—C11	179.8 (5)
C4—C5—C6—C7	177.4 (6)	N3—C9—N1—C11	1.5 (6)
Br2—C5—C6—C7	−3.0 (8)	C6—C7—N1—C9	−100.4 (6)
C1—C6—C7—N1	−57.5 (7)	C6—C7—N1—C11	79.0 (7)
C5—C6—C7—N1	126.1 (6)	N2—C11—N1—C9	118.4 (5)
C6—C1—C8—N2	60.3 (7)	C12—C11—N1—C9	−114.9 (5)
C2—C1—C8—N2	−122.3 (6)	C18—C11—N1—C9	9.4 (6)
N2—C11—C12—C17	−35.8 (7)	N2—C11—N1—C7	−61.0 (6)
N1—C11—C12—C17	−161.9 (5)	C12—C11—N1—C7	65.7 (7)
C18—C11—C12—C17	83.1 (7)	C18—C11—N1—C7	−170.0 (5)
N2—C11—C12—C13	148.4 (6)	O2—C10—N2—C11	171.3 (6)
N1—C11—C12—C13	22.3 (7)	N4—C10—N2—C11	−10.6 (6)
C18—C11—C12—C13	−92.6 (7)	O2—C10—N2—C8	21.8 (9)
C17—C12—C13—C14	−2.3 (10)	N4—C10—N2—C8	−160.2 (5)
C11—C12—C13—C14	173.4 (6)	N1—C11—N2—C10	−90.4 (5)
C12—C13—C14—C15	1.5 (11)	C12—C11—N2—C10	143.4 (5)
C13—C14—C15—C16	−0.2 (13)	C18—C11—N2—C10	17.1 (6)
C14—C15—C16—C17	−0.2 (13)	N1—C11—N2—C8	59.1 (6)
C13—C12—C17—C16	1.9 (10)	C12—C11—N2—C8	−67.1 (6)
C11—C12—C17—C16	−174.0 (6)	C18—C11—N2—C8	166.6 (5)
C15—C16—C17—C12	−0.6 (11)	C1—C8—N2—C10	68.6 (7)
N2—C11—C18—N3	−130.9 (4)	C1—C8—N2—C11	−78.1 (6)
N1—C11—C18—N3	−15.7 (5)	O1—C9—N3—C18	168.2 (6)
C12—C11—C18—N3	105.2 (5)	N1—C9—N3—C18	−13.6 (6)
N2—C11—C18—N4	−16.2 (5)	N4—C18—N3—C9	−86.3 (6)
N1—C11—C18—N4	99.1 (5)	C19—C18—N3—C9	145.2 (5)
C12—C11—C18—N4	−140.1 (5)	C11—C18—N3—C9	18.5 (6)
N2—C11—C18—C19	106.2 (6)	O2—C10—N4—C18	176.2 (6)
N1—C11—C18—C19	−138.5 (5)	N2—C10—N4—C18	−1.7 (7)
C12—C11—C18—C19	−17.7 (7)	N3—C18—N4—C10	118.1 (6)
N3—C18—C19—C20	−55.9 (7)	C19—C18—N4—C10	−114.1 (6)
N4—C18—C19—C20	176.4 (6)	C11—C18—N4—C10	11.5 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O1^i	0.93	2.58	3.432 (9)	152
N4—H4A···O2^ii	0.86	2.08	2.901 (6)	158
N3—H3C···O3^ii	0.86	2.46	2.950 (7)	117
O3—H3B···O1^iii	0.88 (5)	1.91 (5)	2.786 (6)	171 (5)

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