Different cationic forms of (–)-cytisine in the crystal structures of its simple inorganic salts

The crystal structures of 13 simple salts of cytisine, an alkaloid isolated from the seeds of Laburnum anagyroides, have been determined, namely cytisinium (6-oxo-7,11-di­aza­tri­cyclo­[7.3.1.0^2,7]trideca-2,4-dien-11-ium) bromide, C₁₁H₁₅N₂O⁺·Br⁻, cytisinium iodide, C₁₁H₁₅N₂O⁺·I⁻, cytisinium perchlorate, C₁₁H₁₅N₂O⁺·ClO₄⁻, cytisinium iodide triiodide, C₁₁H₁₅N₂O⁺·I⁻·I₃⁻, cyti­sinium chlo­ride monohydrate, C₁₁H₁₅N₂O⁺·Cl⁻·H₂O, cytisinium iodide monohydrate, C₁₁H₁₅N₂O⁺·I⁻·H₂O, cytisinium nitrate monohydrate, C₁₁H₁₅N₂O⁺·NO₃⁻·H₂O, hydrogen dicytisinium tribromide, C₂₂H₃₁N₄O₂³⁺·3Br⁻, hydrogen dicytisinium triiodide, C₂₂H₃₁N₄O₂³⁺·3I⁻, hydrogen dicytisinium triiodide diiodide, C₂₂H₃₁N₄O₂³⁺·I₃⁻·2I⁻, hydrogen dicytisinium bis­(tri­iodide) iodide, C₂₂H₃₁N₄O₂³⁺·2I₃⁻·I⁻, cytisinediium (6-oxidaniumyl­idene-7,11-di­aza­tri­cyclo­[7.3.1.0^2,7]trideca-2,4-dien-11-ium) bis­(perchlorate), C₁₁H₁₆N₂O²⁺·2ClO₄⁻, and cytisinediium dichloride trihydrate, C₁₁H₁₆N₂O²⁺·2Cl⁻·3H₂O. Cytisine has two potential protonation sites, i.e. the N atom of the piperidine ring and the carbonyl O atom of the pyridone ring. Three forms of the cytisinium cation were identified, namely the monocation, which is always protonated at the N atom, the dication, which utilizes both protonation sites, and the third form, which contains two cytisine moieties connected by very short and linear O...H...O hydrogen bonds, with an O...O distance of approximately 2.4 Å. This third form may therefore be regarded as a 3+ species, or sesqui-cation, and is observed solely in the salts with bromide, iodide or triiodide (heavier halogen) anions. The cation is quite rigid and all 19 cytisinium fragments in the studied series have very similar conformations. The crystal structures are determined mainly by Coulombic inter­actions and hydrogen bonds, and the latter form is determined by different networks. Additionally, some anion–π and lone-pair...π secondary inter­actions are identified in almost all of the crystal structures. Hirshfeld surface analysis generally confirms the role of different inter­actions in the determination of the crystal architecture.

Computing details

Data collection: (CrysAlis PRO; Agilent, 2014) for (1), (4), (5), (6), (10), (12); CrysAlis PRO (Rigaku OD, 2015) for (2), (9), (11), (13); (CrysAlis PRO; Agilent, 2013) for (3), (7); CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for (8). Cell refinement: (CrysAlis PRO; Agilent, 2014) for (1), (4), (5), (6), (10), (12); CrysAlis PRO (Rigaku OD, 2015) for (2), (9), (11), (13); (CrysAlis PRO; Agilent, 2013) for (3), (7); CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for (8). Data reduction: (CrysAlis PRO; Agilent, 2014) for (1), (4), (5), (6), (10), (12); CrysAlis PRO (Rigaku OD, 2015) for (2), (9), (11), (13); (CrysAlis PRO; Agilent, 2013) for (3), (7); CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for (8). For all structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b) for (1), (3), (4), (6), (10), (11), (12), (13); SHELXL2014 (Sheldrick, 2015b) for (2), (5), (7), (8), (9). For all structures, molecular graphics: Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015b) for (1), (3), (4), (6), (10), (11), (12), (13); SHELXL2014 (Sheldrick, 2015b) for (2), (5), (7), (8), (9).

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium bromide (1)

Crystal data

C11H15N2O^+·Br^−	Dx = 1.633 Mg m^−3
Mr = 271.16	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P32	Cell parameters from 4385 reflections
a = 7.3942 (2) Å	θ = 3.2–27.9°
c = 17.4657 (4) Å	µ = 3.70 mm^−1
V = 826.99 (5) Å^3	T = 100 K
Z = 3	Plate, colourless
F(000) = 414	0.2 × 0.2 × 0.07 mm

Data collection

Agilent Xcalibur Eos diffractometer	2153 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1987 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 16.1544 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −9→9
Tmin = 0.770, Tmax = 1.000	l = −21→21
9856 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0115P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.047	(Δ/σ)max = 0.006
S = 1.00	Δρmax = 0.55 e Å^−3
2153 reflections	Δρmin = −0.25 e Å^−3
144 parameters	Absolute structure: Flack x determined using 919 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
1 restraint	Absolute structure parameter: −0.016 (7)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
N1	0.6853 (6)	0.2130 (6)	0.19366 (19)	0.0123 (9)
C2	0.5578 (8)	0.2546 (8)	0.1481 (3)	0.0163 (11)
O2	0.5559 (5)	0.4212 (5)	0.15762 (17)	0.0177 (8)
C3	0.4296 (8)	0.0970 (9)	0.0939 (3)	0.0203 (12)
H3	0.3468	0.1210	0.0601	0.024*
C4	0.4280 (8)	−0.0863 (9)	0.0915 (3)	0.0188 (13)
H4	0.3399	−0.1896	0.0574	0.023*
C5	0.5561 (8)	−0.1216 (8)	0.1392 (3)	0.0202 (13)
H5	0.5550	−0.2477	0.1364	0.024*
C6	0.6844 (8)	0.0270 (7)	0.1906 (3)	0.0149 (11)
C7	0.8315 (7)	−0.0038 (9)	0.2406 (3)	0.0191 (12)
H7	0.7693	−0.1534	0.2512	0.023*
C8	0.8693 (8)	0.1110 (8)	0.3166 (3)	0.0212 (12)
H8A	0.7393	0.0584	0.3446	0.025*
H8B	0.9667	0.0913	0.3477	0.025*
C9	0.9594 (8)	0.3421 (8)	0.2978 (3)	0.0179 (11)
H9	0.9859	0.4180	0.3463	0.021*
C10	0.8011 (7)	0.3734 (7)	0.2532 (2)	0.0173 (11)
H10A	0.7011	0.3740	0.2890	0.021*
H10B	0.8730	0.5095	0.2289	0.021*
C11	1.1688 (8)	0.4239 (8)	0.2567 (3)	0.0219 (13)
H11A	1.2230	0.5692	0.2430	0.026*
H11B	1.2679	0.4170	0.2913	0.026*
N12	1.1493 (7)	0.3022 (7)	0.1866 (2)	0.0164 (10)
H12A	1.079 (7)	0.330 (6)	0.146 (3)	0.024 (14)*
H12B	1.263 (8)	0.329 (8)	0.170 (3)	0.017 (14)*
C13	1.0403 (7)	0.0708 (8)	0.1989 (3)	0.0171 (11)
H13A	1.1284	0.0356	0.2291	0.021*
H13B	1.0149	0.0004	0.1499	0.021*
Br1	1.05341 (7)	0.35979 (7)	0.01435 (2)	0.02068 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.011 (2)	0.016 (2)	0.011 (2)	0.008 (2)	0.0022 (16)	−0.0001 (17)
C2	0.012 (3)	0.021 (3)	0.016 (3)	0.009 (2)	0.004 (2)	0.003 (2)
O2	0.0153 (18)	0.0168 (19)	0.0251 (19)	0.0110 (16)	0.0009 (14)	0.0008 (15)
C3	0.012 (3)	0.031 (3)	0.017 (3)	0.009 (3)	0.001 (2)	−0.001 (2)
C4	0.014 (3)	0.020 (3)	0.016 (3)	0.003 (2)	0.004 (2)	−0.005 (2)
C5	0.018 (3)	0.016 (3)	0.025 (3)	0.008 (3)	0.007 (2)	−0.003 (2)
C6	0.015 (3)	0.017 (3)	0.016 (3)	0.011 (2)	0.004 (2)	0.004 (2)
C7	0.018 (3)	0.021 (3)	0.023 (3)	0.013 (3)	0.008 (2)	0.011 (2)
C8	0.021 (3)	0.034 (3)	0.016 (3)	0.019 (3)	0.005 (2)	0.007 (2)
C9	0.018 (3)	0.029 (3)	0.008 (2)	0.013 (3)	−0.004 (2)	−0.005 (2)
C10	0.014 (3)	0.015 (3)	0.019 (3)	0.005 (2)	−0.003 (2)	−0.007 (2)
C11	0.021 (3)	0.027 (3)	0.014 (3)	0.009 (3)	−0.004 (2)	−0.006 (2)
N12	0.012 (2)	0.027 (3)	0.015 (2)	0.013 (2)	0.004 (2)	0.0036 (19)
C13	0.022 (3)	0.023 (3)	0.015 (2)	0.018 (3)	0.001 (2)	0.000 (2)
Br1	0.0277 (3)	0.0181 (3)	0.0160 (2)	0.0113 (3)	−0.0041 (3)	−0.0011 (2)

Geometric parameters (Å, º)

N1—C6	1.373 (6)	C8—H8A	0.9700
N1—C2	1.381 (6)	C8—H8B	0.9700
N1—C10	1.486 (5)	C9—C10	1.516 (6)
C2—O2	1.250 (5)	C9—C11	1.530 (7)
C2—C3	1.431 (7)	C9—H9	0.9800
C3—C4	1.350 (7)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.381 (7)	C11—N12	1.484 (6)
C4—H4	0.9300	C11—H11A	0.9700
C5—C6	1.368 (7)	C11—H11B	0.9700
C5—H5	0.9300	N12—C13	1.498 (6)
C6—C7	1.499 (6)	N12—H12A	0.96 (5)
C7—C8	1.524 (6)	N12—H12B	0.81 (5)
C7—C13	1.538 (6)	C13—H13A	0.9700
C7—H7	0.9800	C13—H13B	0.9700
C8—C9	1.528 (7)
C6—N1—C2	122.6 (4)	C10—C9—C8	110.1 (4)
C6—N1—C10	122.6 (4)	C10—C9—C11	113.9 (4)
C2—N1—C10	114.3 (4)	C8—C9—C11	109.4 (4)
O2—C2—N1	119.2 (4)	C10—C9—H9	107.8
O2—C2—C3	124.2 (5)	C8—C9—H9	107.8
N1—C2—C3	116.6 (4)	C11—C9—H9	107.8
C4—C3—C2	120.6 (5)	N1—C10—C9	114.7 (4)
C4—C3—H3	119.7	N1—C10—H10A	108.6
C2—C3—H3	119.7	C9—C10—H10A	108.6
C3—C4—C5	120.5 (5)	N1—C10—H10B	108.6
C3—C4—H4	119.7	C9—C10—H10B	108.6
C5—C4—H4	119.7	H10A—C10—H10B	107.6
C6—C5—C4	120.7 (5)	N12—C11—C9	112.0 (4)
C6—C5—H5	119.7	N12—C11—H11A	109.2
C4—C5—H5	119.7	C9—C11—H11A	109.2
C5—C6—N1	119.0 (4)	N12—C11—H11B	109.2
C5—C6—C7	121.7 (4)	C9—C11—H11B	109.2
N1—C6—C7	119.3 (4)	H11A—C11—H11B	107.9
C6—C7—C8	111.5 (4)	C11—N12—C13	114.0 (4)
C6—C7—C13	110.1 (4)	C11—N12—H12A	113 (3)
C8—C7—C13	109.9 (4)	C13—N12—H12A	108 (2)
C6—C7—H7	108.4	C11—N12—H12B	112 (4)
C8—C7—H7	108.4	C13—N12—H12B	103 (3)
C13—C7—H7	108.4	H12A—N12—H12B	106 (4)
C9—C8—C7	107.0 (4)	N12—C13—C7	110.4 (4)
C9—C8—H8A	110.3	N12—C13—H13A	109.6
C7—C8—H8A	110.3	C7—C13—H13A	109.6
C9—C8—H8B	110.3	N12—C13—H13B	109.6
C7—C8—H8B	110.3	C7—C13—H13B	109.6
H8A—C8—H8B	108.6	H13A—C13—H13B	108.1
C6—N1—C2—O2	175.0 (4)	C5—C6—C7—C13	87.5 (6)
C10—N1—C2—O2	3.0 (6)	N1—C6—C7—C13	−89.2 (5)
C6—N1—C2—C3	−3.0 (6)	C6—C7—C8—C9	−58.9 (5)
C10—N1—C2—C3	−175.0 (4)	C13—C7—C8—C9	63.5 (5)
O2—C2—C3—C4	−174.4 (5)	C7—C8—C9—C10	63.4 (5)
N1—C2—C3—C4	3.5 (7)	C7—C8—C9—C11	−62.4 (5)
C2—C3—C4—C5	−2.5 (7)	C6—N1—C10—C9	14.5 (6)
C3—C4—C5—C6	1.0 (8)	C2—N1—C10—C9	−173.5 (4)
C4—C5—C6—N1	−0.5 (7)	C8—C9—C10—N1	−41.3 (5)
C4—C5—C6—C7	−177.3 (4)	C11—C9—C10—N1	81.9 (5)
C2—N1—C6—C5	1.6 (7)	C10—C9—C11—N12	−67.0 (6)
C10—N1—C6—C5	173.0 (4)	C8—C9—C11—N12	56.6 (5)
C2—N1—C6—C7	178.5 (4)	C9—C11—N12—C13	−51.1 (6)
C10—N1—C6—C7	−10.2 (6)	C11—N12—C13—C7	51.0 (6)
C5—C6—C7—C8	−150.1 (4)	C6—C7—C13—N12	65.8 (5)
N1—C6—C7—C8	33.1 (6)	C8—C7—C13—N12	−57.5 (5)

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium iodide (2)

Crystal data

C11H15N2O^+·I^−	Dx = 1.747 Mg m^−3
Mr = 318.15	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P32	Cell parameters from 1290 reflections
a = 7.5220 (2) Å	θ = 3.1–26.3°
c = 18.5124 (4) Å	µ = 2.63 mm^−1
V = 907.11 (5) Å^3	T = 295 K
Z = 3	Prism, colourless
F(000) = 468	0.2 × 0.2 × 0.15 mm

Data collection

Agilent Xcalibur Eos diffractometer	1511 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1402 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
Detector resolution: 16.1544 pixels mm^-1	θmax = 28.2°, θmin = 3.1°
ω scan	h = −3→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −9→5
Tmin = 0.265, Tmax = 1.000	l = −14→24
1906 measured reflections

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)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0212P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.049	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.28 e Å^−3
1511 reflections	Δρmin = −0.45 e Å^−3
136 parameters	Absolute structure: Flack x determined using 266 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.07 (2)

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
N1	0.7054 (7)	0.2179 (7)	0.1927 (2)	0.0368 (12)
C2	0.5763 (9)	0.2615 (10)	0.1511 (3)	0.0397 (15)
O2	0.5728 (6)	0.4214 (7)	0.1637 (2)	0.0565 (12)
C3	0.4564 (11)	0.1118 (14)	0.0986 (4)	0.057 (2)
H3	0.3753	0.1375	0.0673	0.069*
C4	0.4565 (12)	−0.0637 (14)	0.0929 (4)	0.063 (2)
H4	0.3730	−0.1602	0.0588	0.075*
C5	0.5803 (12)	−0.1050 (12)	0.1375 (4)	0.061 (2)
H5	0.5765	−0.2301	0.1337	0.074*
C6	0.7082 (10)	0.0378 (10)	0.1872 (4)	0.0464 (16)
C7	0.8506 (11)	0.0019 (12)	0.2339 (4)	0.059 (2)
H7	0.7883	−0.1458	0.2427	0.071*
C8	0.8843 (12)	0.1111 (14)	0.3065 (4)	0.071 (2)
H8A	0.7553	0.0575	0.3322	0.085*
H8B	0.9788	0.0901	0.3360	0.085*
C9	0.9725 (11)	0.3374 (14)	0.2908 (4)	0.061 (2)
H9	0.9965	0.4086	0.3372	0.073*
C10	0.8227 (11)	0.3741 (11)	0.2486 (3)	0.0491 (17)
H10A	0.7263	0.3793	0.2821	0.059*
H10B	0.8976	0.5073	0.2254	0.059*
C11	1.1817 (12)	0.4187 (13)	0.2534 (4)	0.065 (2)
H11A	1.2366	0.5625	0.2417	0.078*
H11B	1.2761	0.4092	0.2868	0.078*
N12	1.1698 (8)	0.3057 (9)	0.1869 (3)	0.0510 (14)
H12A	1.2968	0.3458	0.1719	0.061*
H12B	1.1086	0.3394	0.1528	0.061*
C13	1.0566 (11)	0.0775 (11)	0.1951 (4)	0.0563 (19)
H13A	1.1400	0.0363	0.2224	0.068*
H13B	1.0320	0.0142	0.1478	0.068*
I1	1.06308 (7)	0.37323 (6)	0.01435 (2)	0.05643 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.030 (2)	0.045 (3)	0.040 (3)	0.022 (3)	0.004 (2)	−0.002 (2)
C2	0.024 (3)	0.050 (4)	0.042 (4)	0.016 (3)	0.005 (3)	0.001 (3)
O2	0.047 (3)	0.060 (3)	0.077 (3)	0.037 (2)	−0.001 (2)	0.002 (3)
C3	0.039 (4)	0.086 (6)	0.041 (4)	0.027 (4)	0.001 (3)	−0.005 (4)
C4	0.042 (4)	0.065 (5)	0.055 (4)	0.006 (4)	0.002 (4)	−0.023 (4)
C5	0.052 (5)	0.047 (4)	0.077 (5)	0.019 (4)	0.026 (4)	−0.003 (4)
C6	0.041 (4)	0.042 (4)	0.059 (4)	0.022 (3)	0.015 (3)	0.002 (3)
C7	0.058 (5)	0.066 (5)	0.070 (5)	0.043 (4)	0.017 (4)	0.025 (4)
C8	0.073 (5)	0.125 (8)	0.046 (4)	0.073 (6)	0.014 (4)	0.021 (5)
C9	0.052 (5)	0.102 (6)	0.038 (4)	0.045 (5)	−0.007 (3)	−0.022 (4)
C10	0.045 (4)	0.056 (4)	0.048 (4)	0.026 (3)	−0.007 (3)	−0.017 (3)
C11	0.055 (5)	0.101 (6)	0.053 (4)	0.050 (5)	−0.013 (4)	−0.020 (5)
N12	0.040 (3)	0.076 (4)	0.046 (3)	0.036 (3)	−0.002 (2)	0.001 (3)
C13	0.065 (5)	0.075 (5)	0.054 (4)	0.054 (4)	0.012 (4)	0.017 (4)
I1	0.0701 (3)	0.0469 (3)	0.0470 (2)	0.0253 (3)	−0.0131 (3)	−0.0026 (2)

Geometric parameters (Å, º)

N1—C6	1.369 (8)	C8—H8A	0.9700
N1—C2	1.401 (7)	C8—H8B	0.9700
N1—C10	1.481 (7)	C9—C10	1.506 (9)
C2—O2	1.238 (8)	C9—C11	1.538 (10)
C2—C3	1.417 (10)	C9—H9	0.9800
C3—C4	1.324 (12)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.391 (10)	C11—N12	1.474 (8)
C4—H4	0.9300	C11—H11A	0.9700
C5—C6	1.376 (10)	C11—H11B	0.9700
C5—H5	0.9300	N12—C13	1.494 (8)
C6—C7	1.502 (9)	N12—H12A	0.8900
C7—C8	1.528 (10)	N12—H12B	0.8900
C7—C13	1.536 (9)	C13—H13A	0.9700
C7—H7	0.9800	C13—H13B	0.9700
C8—C9	1.514 (11)
C6—N1—C2	123.1 (5)	C10—C9—C8	111.0 (6)
C6—N1—C10	122.6 (5)	C10—C9—C11	113.8 (6)
C2—N1—C10	114.0 (5)	C8—C9—C11	108.6 (7)
O2—C2—N1	118.5 (6)	C10—C9—H9	107.7
O2—C2—C3	125.9 (7)	C8—C9—H9	107.7
N1—C2—C3	115.5 (6)	C11—C9—H9	107.7
C4—C3—C2	122.0 (7)	N1—C10—C9	114.9 (6)
C4—C3—H3	119.0	N1—C10—H10A	108.5
C2—C3—H3	119.0	C9—C10—H10A	108.5
C3—C4—C5	120.6 (7)	N1—C10—H10B	108.5
C3—C4—H4	119.7	C9—C10—H10B	108.5
C5—C4—H4	119.7	H10A—C10—H10B	107.5
C6—C5—C4	120.5 (7)	N12—C11—C9	113.1 (6)
C6—C5—H5	119.8	N12—C11—H11A	109.0
C4—C5—H5	119.8	C9—C11—H11A	109.0
N1—C6—C5	118.1 (6)	N12—C11—H11B	109.0
N1—C6—C7	120.0 (6)	C9—C11—H11B	109.0
C5—C6—C7	121.8 (6)	H11A—C11—H11B	107.8
C6—C7—C8	110.5 (6)	C11—N12—C13	114.4 (5)
C6—C7—C13	110.0 (6)	C11—N12—H12A	108.7
C8—C7—C13	110.3 (7)	C13—N12—H12A	108.7
C6—C7—H7	108.7	C11—N12—H12B	108.7
C8—C7—H7	108.7	C13—N12—H12B	108.7
C13—C7—H7	108.7	H12A—N12—H12B	107.6
C9—C8—C7	107.3 (6)	N12—C13—C7	111.3 (5)
C9—C8—H8A	110.2	N12—C13—H13A	109.4
C7—C8—H8A	110.2	C7—C13—H13A	109.4
C9—C8—H8B	110.2	N12—C13—H13B	109.4
C7—C8—H8B	110.2	C7—C13—H13B	109.4
H8A—C8—H8B	108.5	H13A—C13—H13B	108.0
C6—N1—C2—O2	174.4 (5)	N1—C6—C7—C13	−90.6 (8)
C10—N1—C2—O2	0.6 (8)	C5—C6—C7—C13	88.4 (8)
C6—N1—C2—C3	−4.2 (8)	C6—C7—C8—C9	−58.6 (8)
C10—N1—C2—C3	−178.0 (5)	C13—C7—C8—C9	63.3 (7)
O2—C2—C3—C4	−174.0 (7)	C7—C8—C9—C10	63.2 (8)
N1—C2—C3—C4	4.5 (9)	C7—C8—C9—C11	−62.7 (7)
C2—C3—C4—C5	−1.8 (11)	C6—N1—C10—C9	9.9 (9)
C3—C4—C5—C6	−1.5 (11)	C2—N1—C10—C9	−176.3 (6)
C2—N1—C6—C5	1.1 (9)	C8—C9—C10—N1	−38.7 (8)
C10—N1—C6—C5	174.4 (6)	C11—C9—C10—N1	84.2 (8)
C2—N1—C6—C7	−179.8 (5)	C10—C9—C11—N12	−67.6 (9)
C10—N1—C6—C7	−6.5 (9)	C8—C9—C11—N12	56.6 (8)
C4—C5—C6—N1	1.8 (9)	C9—C11—N12—C13	−49.3 (8)
C4—C5—C6—C7	−177.3 (6)	C11—N12—C13—C7	47.9 (7)
N1—C6—C7—C8	31.4 (9)	C6—C7—C13—N12	67.1 (8)
C5—C6—C7—C8	−149.5 (6)	C8—C7—C13—N12	−55.1 (7)

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium perchlorate (3)

Crystal data

C11H15N2O^+·ClO4^−	Dx = 1.555 Mg m^−3
Mr = 290.70	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1639 reflections
a = 6.8719 (3) Å	θ = 3.3–28.6°
b = 18.8925 (11) Å	µ = 0.33 mm^−1
c = 19.1239 (14) Å	T = 100 K
V = 2482.8 (3) Å^3	Prism, colourless
Z = 8	0.3 × 0.1 × 0.1 mm
F(000) = 1216

Data collection

Agilent Xcalibur Eos diffractometer	3618 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2887 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.1544 pixels mm^-1	θmax = 25.0°, θmin = 3.2°
ω scan	h = −3→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −22→22
Tmin = 0.506, Tmax = 1.000	l = −21→12
4496 measured reflections

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)] = 0.051	w = 1/[σ^2(Fo^2) + (0.060P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.126	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.43 e Å^−3
3618 reflections	Δρmin = −0.45 e Å^−3
343 parameters	Absolute structure: Flack x determined using 865 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.04 (7)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
N1A	0.4720 (7)	0.1354 (3)	0.2282 (2)	0.0200 (11)
C2A	0.4944 (8)	0.0904 (3)	0.1709 (3)	0.0215 (15)
O2A	0.5489 (7)	0.1171 (2)	0.1148 (2)	0.0272 (10)
C3A	0.4488 (9)	0.0179 (3)	0.1817 (4)	0.0241 (14)
H3A	0.4622	−0.0147	0.1442	0.029*
C4A	0.3868 (9)	−0.0051 (3)	0.2447 (4)	0.0306 (18)
H4A	0.3574	−0.0538	0.2510	0.037*
C5A	0.3651 (9)	0.0421 (3)	0.3012 (4)	0.0266 (16)
H5A	0.3202	0.0254	0.3452	0.032*
C6A	0.4092 (8)	0.1118 (3)	0.2921 (3)	0.0220 (15)
C7A	0.3912 (9)	0.1642 (3)	0.3509 (3)	0.0241 (15)
H7A	0.2861	0.1472	0.3829	0.029*
C8A	0.3319 (10)	0.2368 (3)	0.3233 (4)	0.0281 (16)
H8A1	0.3151	0.2706	0.3624	0.034*
H8A2	0.2078	0.2336	0.2972	0.034*
C9A	0.4963 (8)	0.2611 (3)	0.2749 (3)	0.0239 (15)
H9A	0.4611	0.3091	0.2570	0.029*
C10A	0.5104 (9)	0.2116 (3)	0.2117 (3)	0.0211 (14)
H10A	0.4160	0.2274	0.1758	0.025*
H10B	0.6423	0.2157	0.1913	0.025*
C11A	0.6865 (9)	0.2684 (3)	0.3160 (3)	0.0247 (15)
H11A	0.7923	0.2824	0.2837	0.030*
H11B	0.6720	0.3061	0.3515	0.030*
N12A	0.7411 (7)	0.1999 (3)	0.3519 (3)	0.0237 (13)
H12A	0.7829	0.1651	0.3162	0.028*
H12B	0.8527	0.2086	0.3835	0.028*
C13A	0.5781 (9)	0.1695 (3)	0.3930 (3)	0.0276 (15)
H13A	0.5548	0.1993	0.4347	0.033*
H13B	0.6153	0.1216	0.4094	0.033*
N1B	0.9786 (7)	0.0717 (2)	0.1453 (3)	0.0188 (12)
C2B	0.9378 (9)	0.0750 (3)	0.2158 (3)	0.0213 (14)
O2B	0.9336 (6)	0.1350 (2)	0.2447 (2)	0.0241 (10)
C3B	0.9012 (9)	0.0104 (3)	0.2497 (4)	0.0260 (16)
H3B	0.8746	0.0102	0.2985	0.031*
C4B	0.9031 (8)	−0.0517 (3)	0.2142 (4)	0.0286 (16)
H4B	0.8774	−0.0947	0.2382	0.034*
C5B	0.9422 (9)	−0.0530 (3)	0.1431 (3)	0.0231 (14)
H5B	0.9407	−0.0967	0.1185	0.028*
C6B	0.9831 (8)	0.0087 (3)	0.1083 (3)	0.0215 (14)
C7B	1.0252 (9)	0.0099 (3)	0.0328 (3)	0.0223 (15)
H7B	1.0895	−0.0359	0.0205	0.027*
C8B	1.1675 (8)	0.0698 (3)	0.0144 (4)	0.0258 (16)
H8B1	1.2901	0.0645	0.0410	0.031*
H8B2	1.1982	0.0690	−0.0362	0.031*
C9B	1.0646 (9)	0.1390 (3)	0.0341 (3)	0.0226 (14)
H9B	1.1549	0.1789	0.0227	0.027*
C10B	1.0264 (8)	0.1411 (3)	0.1120 (3)	0.0204 (14)
H10C	1.1430	0.1607	0.1354	0.024*
H10D	0.9174	0.1741	0.1208	0.024*
C11B	0.8836 (8)	0.1479 (3)	−0.0105 (3)	0.0228 (14)
H11C	0.8166	0.1923	0.0028	0.027*
H11D	0.9216	0.1516	−0.0603	0.027*
N12B	0.7467 (7)	0.0868 (2)	−0.0014 (3)	0.0186 (11)
H12C	0.6923	0.0880	0.0465	0.022*
H12D	0.6373	0.0920	−0.0347	0.022*
C13B	0.8426 (9)	0.0170 (3)	−0.0131 (4)	0.0246 (15)
H13C	0.8793	0.0124	−0.0630	0.030*
H13D	0.7502	−0.0215	−0.0017	0.030*
Cl1	0.9350 (2)	0.33923 (7)	0.13214 (8)	0.0230 (4)
O11	0.7365 (6)	0.3468 (2)	0.1537 (2)	0.0394 (12)
O12	1.0433 (7)	0.3017 (2)	0.1842 (2)	0.0325 (11)
O13	0.9445 (7)	0.3030 (2)	0.0660 (2)	0.0278 (11)
O14	1.0165 (6)	0.4093 (2)	0.1227 (2)	0.0272 (11)
Cl2	0.0480 (2)	0.14018 (7)	0.50096 (8)	0.0241 (4)
O21	−0.0746 (8)	0.1228 (3)	0.5580 (3)	0.0461 (14)
O22	−0.0107 (7)	0.2069 (2)	0.4713 (3)	0.0426 (14)
O23	0.0343 (8)	0.0863 (2)	0.4482 (3)	0.0440 (14)
O24	0.2452 (6)	0.1475 (2)	0.5245 (3)	0.0393 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.017 (3)	0.018 (3)	0.025 (3)	−0.002 (2)	−0.002 (2)	0.001 (2)
C2A	0.016 (4)	0.024 (3)	0.025 (4)	0.003 (3)	−0.001 (3)	−0.005 (3)
O2A	0.024 (2)	0.030 (2)	0.027 (3)	0.003 (2)	0.001 (2)	0.000 (2)
C3A	0.018 (3)	0.019 (3)	0.036 (4)	0.001 (3)	−0.007 (3)	−0.005 (3)
C4A	0.015 (4)	0.017 (3)	0.060 (5)	0.001 (3)	−0.005 (3)	0.011 (4)
C5A	0.018 (3)	0.024 (3)	0.038 (4)	−0.005 (3)	0.001 (3)	0.007 (3)
C6A	0.011 (3)	0.022 (3)	0.032 (4)	−0.001 (3)	−0.002 (3)	−0.001 (3)
C7A	0.023 (4)	0.024 (3)	0.025 (4)	−0.005 (3)	0.006 (3)	−0.004 (3)
C8A	0.024 (4)	0.025 (3)	0.035 (4)	0.000 (3)	0.005 (3)	−0.004 (3)
C9A	0.023 (4)	0.015 (3)	0.033 (4)	0.000 (3)	0.000 (3)	0.008 (3)
C10A	0.022 (4)	0.014 (3)	0.027 (3)	−0.002 (3)	0.000 (3)	0.004 (3)
C11A	0.028 (4)	0.020 (3)	0.026 (4)	−0.004 (3)	0.002 (3)	−0.007 (3)
N12A	0.019 (3)	0.024 (3)	0.029 (3)	−0.001 (2)	−0.002 (2)	−0.002 (2)
C13A	0.027 (4)	0.025 (3)	0.031 (4)	−0.005 (3)	0.002 (3)	0.004 (3)
N1B	0.019 (3)	0.011 (2)	0.027 (3)	0.000 (2)	−0.001 (2)	0.004 (2)
C2B	0.012 (3)	0.025 (3)	0.026 (4)	0.003 (3)	−0.001 (3)	−0.002 (3)
O2B	0.023 (2)	0.021 (2)	0.028 (2)	−0.001 (2)	0.0013 (19)	−0.004 (2)
C3B	0.015 (4)	0.026 (3)	0.037 (4)	0.000 (3)	0.002 (3)	0.008 (3)
C4B	0.015 (3)	0.021 (3)	0.049 (5)	−0.005 (3)	−0.005 (3)	0.015 (3)
C5B	0.022 (3)	0.016 (3)	0.032 (4)	−0.004 (3)	−0.009 (3)	−0.003 (3)
C6B	0.013 (3)	0.017 (3)	0.034 (4)	0.001 (3)	−0.001 (3)	0.003 (3)
C7B	0.025 (4)	0.010 (3)	0.032 (4)	0.004 (3)	−0.005 (3)	−0.001 (3)
C8B	0.014 (3)	0.029 (3)	0.035 (4)	0.003 (3)	0.003 (3)	0.000 (3)
C9B	0.021 (3)	0.012 (3)	0.035 (4)	−0.003 (3)	0.002 (3)	0.005 (3)
C10B	0.019 (3)	0.012 (3)	0.030 (3)	−0.005 (3)	−0.004 (3)	−0.001 (3)
C11B	0.028 (3)	0.010 (3)	0.031 (4)	−0.001 (3)	0.001 (3)	0.004 (3)
N12B	0.019 (3)	0.018 (2)	0.018 (3)	0.004 (2)	−0.002 (2)	−0.003 (2)
C13B	0.021 (3)	0.017 (3)	0.035 (4)	−0.001 (3)	−0.004 (3)	−0.003 (3)
Cl1	0.0259 (8)	0.0153 (7)	0.0278 (8)	−0.0024 (7)	0.0024 (7)	0.0008 (7)
O11	0.025 (3)	0.036 (3)	0.057 (3)	−0.001 (2)	0.012 (2)	0.009 (3)
O12	0.042 (3)	0.021 (2)	0.035 (3)	0.004 (2)	−0.008 (2)	0.005 (2)
O13	0.042 (3)	0.020 (2)	0.022 (2)	−0.004 (2)	−0.004 (2)	−0.0051 (19)
O14	0.035 (3)	0.013 (2)	0.033 (3)	−0.0091 (19)	0.003 (2)	0.0000 (19)
Cl2	0.0237 (8)	0.0198 (7)	0.0288 (8)	−0.0022 (7)	0.0028 (7)	−0.0020 (7)
O21	0.054 (4)	0.042 (3)	0.042 (3)	−0.021 (3)	0.025 (3)	−0.009 (2)
O22	0.052 (4)	0.029 (3)	0.047 (3)	0.013 (2)	−0.020 (3)	0.003 (2)
O23	0.051 (3)	0.034 (3)	0.047 (3)	−0.021 (3)	0.016 (3)	−0.019 (2)
O24	0.025 (3)	0.032 (3)	0.060 (4)	0.003 (2)	−0.006 (2)	0.000 (3)

Geometric parameters (Å, º)

N1A—C6A	1.370 (8)	C2B—C3B	1.406 (8)
N1A—C2A	1.396 (8)	C3B—C4B	1.356 (9)
N1A—C10A	1.496 (7)	C3B—H3B	0.9500
C2A—O2A	1.242 (7)	C4B—C5B	1.385 (9)
C2A—C3A	1.421 (8)	C4B—H4B	0.9500
C3A—C4A	1.349 (9)	C5B—C6B	1.371 (8)
C3A—H3A	0.9500	C5B—H5B	0.9500
C4A—C5A	1.409 (10)	C6B—C7B	1.472 (9)
C4A—H4A	0.9500	C7B—C8B	1.536 (8)
C5A—C6A	1.364 (8)	C7B—C13B	1.537 (8)
C5A—H5A	0.9500	C7B—H7B	1.0000
C6A—C7A	1.503 (8)	C8B—C9B	1.534 (8)
C7A—C13A	1.519 (9)	C8B—H8B1	0.9900
C7A—C8A	1.525 (8)	C8B—H8B2	0.9900
C7A—H7A	1.0000	C9B—C10B	1.513 (8)
C8A—C9A	1.530 (9)	C9B—C11B	1.517 (8)
C8A—H8A1	0.9900	C9B—H9B	1.0000
C8A—H8A2	0.9900	C10B—H10C	0.9900
C9A—C10A	1.531 (9)	C10B—H10D	0.9900
C9A—C11A	1.532 (8)	C11B—N12B	1.499 (7)
C9A—H9A	1.0000	C11B—H11C	0.9900
C10A—H10A	0.9900	C11B—H11D	0.9900
C10A—H10B	0.9900	N12B—C13B	1.491 (7)
C11A—N12A	1.511 (8)	N12B—H12C	0.9900
C11A—H11A	0.9900	N12B—H12D	0.9900
C11A—H11B	0.9900	C13B—H13C	0.9900
N12A—C13A	1.484 (8)	C13B—H13D	0.9900
N12A—H12A	0.9900	Cl1—O12	1.431 (4)
N12A—H12B	0.9900	Cl1—O11	1.433 (4)
C13A—H13A	0.9900	Cl1—O13	1.439 (4)
C13A—H13B	0.9900	Cl1—O14	1.448 (4)
N1B—C2B	1.380 (7)	Cl2—O21	1.417 (5)
N1B—C6B	1.386 (7)	Cl2—O24	1.435 (4)
N1B—C10B	1.493 (7)	Cl2—O23	1.437 (5)
C2B—O2B	1.261 (7)	Cl2—O22	1.440 (5)
C6A—N1A—C2A	122.5 (5)	C4B—C3B—C2B	121.2 (6)
C6A—N1A—C10A	123.8 (5)	C4B—C3B—H3B	119.4
C2A—N1A—C10A	113.6 (5)	C2B—C3B—H3B	119.4
O2A—C2A—N1A	117.7 (5)	C3B—C4B—C5B	120.6 (6)
O2A—C2A—C3A	125.6 (6)	C3B—C4B—H4B	119.7
N1A—C2A—C3A	116.6 (6)	C5B—C4B—H4B	119.7
C4A—C3A—C2A	120.7 (6)	C6B—C5B—C4B	120.1 (6)
C4A—C3A—H3A	119.7	C6B—C5B—H5B	119.9
C2A—C3A—H3A	119.7	C4B—C5B—H5B	119.9
C3A—C4A—C5A	121.0 (6)	C5B—C6B—N1B	118.5 (6)
C3A—C4A—H4A	119.5	C5B—C6B—C7B	122.1 (5)
C5A—C4A—H4A	119.5	N1B—C6B—C7B	119.4 (5)
C6A—C5A—C4A	119.3 (6)	C6B—C7B—C8B	111.2 (5)
C6A—C5A—H5A	120.4	C6B—C7B—C13B	113.6 (5)
C4A—C5A—H5A	120.4	C8B—C7B—C13B	108.9 (5)
C5A—C6A—N1A	119.9 (6)	C6B—C7B—H7B	107.6
C5A—C6A—C7A	121.4 (6)	C8B—C7B—H7B	107.6
N1A—C6A—C7A	118.6 (5)	C13B—C7B—H7B	107.6
C6A—C7A—C13A	111.7 (5)	C9B—C8B—C7B	106.1 (5)
C6A—C7A—C8A	110.8 (5)	C9B—C8B—H8B1	110.5
C13A—C7A—C8A	110.5 (5)	C7B—C8B—H8B1	110.5
C6A—C7A—H7A	107.9	C9B—C8B—H8B2	110.5
C13A—C7A—H7A	107.9	C7B—C8B—H8B2	110.5
C8A—C7A—H7A	107.9	H8B1—C8B—H8B2	108.7
C7A—C8A—C9A	106.3 (5)	C10B—C9B—C11B	114.1 (5)
C7A—C8A—H8A1	110.5	C10B—C9B—C8B	110.1 (5)
C9A—C8A—H8A1	110.5	C11B—C9B—C8B	109.6 (5)
C7A—C8A—H8A2	110.5	C10B—C9B—H9B	107.6
C9A—C8A—H8A2	110.5	C11B—C9B—H9B	107.6
H8A1—C8A—H8A2	108.7	C8B—C9B—H9B	107.6
C8A—C9A—C10A	109.9 (5)	N1B—C10B—C9B	115.8 (5)
C8A—C9A—C11A	110.3 (5)	N1B—C10B—H10C	108.3
C10A—C9A—C11A	113.9 (5)	C9B—C10B—H10C	108.3
C8A—C9A—H9A	107.5	N1B—C10B—H10D	108.3
C10A—C9A—H9A	107.5	C9B—C10B—H10D	108.3
C11A—C9A—H9A	107.5	H10C—C10B—H10D	107.4
N1A—C10A—C9A	114.2 (5)	N12B—C11B—C9B	111.3 (5)
N1A—C10A—H10A	108.7	N12B—C11B—H11C	109.4
C9A—C10A—H10A	108.7	C9B—C11B—H11C	109.4
N1A—C10A—H10B	108.7	N12B—C11B—H11D	109.4
C9A—C10A—H10B	108.7	C9B—C11B—H11D	109.4
H10A—C10A—H10B	107.6	H11C—C11B—H11D	108.0
N12A—C11A—C9A	111.6 (5)	C13B—N12B—C11B	112.7 (4)
N12A—C11A—H11A	109.3	C13B—N12B—H12C	109.0
C9A—C11A—H11A	109.3	C11B—N12B—H12C	109.0
N12A—C11A—H11B	109.3	C13B—N12B—H12D	109.0
C9A—C11A—H11B	109.3	C11B—N12B—H12D	109.0
H11A—C11A—H11B	108.0	H12C—N12B—H12D	107.8
C13A—N12A—C11A	112.6 (5)	N12B—C13B—C7B	110.6 (5)
C13A—N12A—H12A	109.1	N12B—C13B—H13C	109.5
C11A—N12A—H12A	109.1	C7B—C13B—H13C	109.5
C13A—N12A—H12B	109.1	N12B—C13B—H13D	109.5
C11A—N12A—H12B	109.1	C7B—C13B—H13D	109.5
H12A—N12A—H12B	107.8	H13C—C13B—H13D	108.1
N12A—C13A—C7A	112.5 (5)	O12—Cl1—O11	110.1 (3)
N12A—C13A—H13A	109.1	O12—Cl1—O13	110.6 (3)
C7A—C13A—H13A	109.1	O11—Cl1—O13	110.1 (3)
N12A—C13A—H13B	109.1	O12—Cl1—O14	109.8 (3)
C7A—C13A—H13B	109.1	O11—Cl1—O14	108.3 (3)
H13A—C13A—H13B	107.8	O13—Cl1—O14	107.9 (3)
C2B—N1B—C6B	122.8 (5)	O21—Cl2—O24	110.0 (3)
C2B—N1B—C10B	115.0 (5)	O21—Cl2—O23	109.7 (3)
C6B—N1B—C10B	122.2 (5)	O24—Cl2—O23	110.5 (3)
O2B—C2B—N1B	118.3 (5)	O21—Cl2—O22	109.9 (3)
O2B—C2B—C3B	125.0 (6)	O24—Cl2—O22	107.7 (3)
N1B—C2B—C3B	116.7 (5)	O23—Cl2—O22	109.0 (3)
C6A—N1A—C2A—O2A	178.8 (5)	C6B—N1B—C2B—O2B	−178.7 (5)
C10A—N1A—C2A—O2A	2.5 (8)	C10B—N1B—C2B—O2B	3.8 (8)
C6A—N1A—C2A—C3A	−0.1 (8)	C6B—N1B—C2B—C3B	0.4 (9)
C10A—N1A—C2A—C3A	−176.3 (5)	C10B—N1B—C2B—C3B	−177.0 (5)
O2A—C2A—C3A—C4A	−178.6 (6)	O2B—C2B—C3B—C4B	178.0 (6)
N1A—C2A—C3A—C4A	0.1 (9)	N1B—C2B—C3B—C4B	−1.1 (9)
C2A—C3A—C4A—C5A	0.2 (10)	C2B—C3B—C4B—C5B	0.3 (10)
C3A—C4A—C5A—C6A	−0.6 (10)	C3B—C4B—C5B—C6B	1.2 (9)
C4A—C5A—C6A—N1A	0.6 (9)	C4B—C5B—C6B—N1B	−1.8 (9)
C4A—C5A—C6A—C7A	−179.2 (6)	C4B—C5B—C6B—C7B	−179.9 (6)
C2A—N1A—C6A—C5A	−0.3 (9)	C2B—N1B—C6B—C5B	1.0 (9)
C10A—N1A—C6A—C5A	175.6 (5)	C10B—N1B—C6B—C5B	178.3 (5)
C2A—N1A—C6A—C7A	179.5 (5)	C2B—N1B—C6B—C7B	179.1 (5)
C10A—N1A—C6A—C7A	−4.6 (8)	C10B—N1B—C6B—C7B	−3.6 (8)
C5A—C6A—C7A—C13A	89.3 (7)	C5B—C6B—C7B—C8B	−148.7 (6)
N1A—C6A—C7A—C13A	−90.5 (7)	N1B—C6B—C7B—C8B	33.2 (7)
C5A—C6A—C7A—C8A	−147.0 (6)	C5B—C6B—C7B—C13B	87.9 (7)
N1A—C6A—C7A—C8A	33.2 (7)	N1B—C6B—C7B—C13B	−90.2 (6)
C6A—C7A—C8A—C9A	−62.4 (6)	C6B—C7B—C8B—C9B	−62.1 (6)
C13A—C7A—C8A—C9A	62.0 (7)	C13B—C7B—C8B—C9B	63.9 (6)
C7A—C8A—C9A—C10A	64.5 (7)	C7B—C8B—C9B—C10B	62.8 (6)
C7A—C8A—C9A—C11A	−62.0 (7)	C7B—C8B—C9B—C11B	−63.5 (6)
C6A—N1A—C10A—C9A	6.7 (8)	C2B—N1B—C10B—C9B	−177.9 (5)
C2A—N1A—C10A—C9A	−177.1 (5)	C6B—N1B—C10B—C9B	4.6 (8)
C8A—C9A—C10A—N1A	−37.0 (7)	C11B—C9B—C10B—N1B	88.5 (6)
C11A—C9A—C10A—N1A	87.4 (6)	C8B—C9B—C10B—N1B	−35.1 (7)
C8A—C9A—C11A—N12A	57.0 (7)	C10B—C9B—C11B—N12B	−65.6 (6)
C10A—C9A—C11A—N12A	−67.2 (7)	C8B—C9B—C11B—N12B	58.3 (6)
C9A—C11A—N12A—C13A	−50.2 (7)	C9B—C11B—N12B—C13B	−53.0 (7)
C11A—N12A—C13A—C7A	50.5 (7)	C11B—N12B—C13B—C7B	53.4 (7)
C6A—C7A—C13A—N12A	66.3 (7)	C6B—C7B—C13B—N12B	65.1 (6)
C8A—C7A—C13A—N12A	−57.5 (7)	C8B—C7B—C13B—N12B	−59.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7A—H7A···O23	1.00	2.42	3.413 (8)	170
N12A—H12B···O22^i	0.99	1.92	2.853 (7)	155
N12A—H12A···O2B	0.99	1.81	2.730 (6)	154
C3B—H3B···O14^ii	0.95	2.54	3.150 (8)	122
C7B—H7B···O24^iii	1.00	2.40	3.371 (7)	165
C11B—H11C···O13	0.99	2.57	3.302 (7)	131
N12B—H12C···O2A	0.99	1.72	2.666 (7)	157
N12B—H12D···O13^iv	0.99	2.46	3.190 (6)	130
N12B—H12D···O14^iv	0.99	1.88	2.808 (6)	156
C13B—H13D···O21^v	0.99	2.53	3.495 (8)	164
C13B—H13D···O23^v	0.99	2.50	3.326 (7)	141

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

Bis(6-oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium) iodide triiodide (4)

Crystal data

2C11H15N2O^+·I^−·I3^−	Z = 1
Mr = 890.10	F(000) = 418
Triclinic, P1	Dx = 2.219 Mg m^−3
a = 7.5105 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5353 (4) Å	Cell parameters from 4154 reflections
c = 13.8994 (7) Å	θ = 3.2–28.7°
α = 79.612 (4)°	µ = 4.71 mm^−1
β = 75.806 (4)°	T = 100 K
γ = 61.115 (5)°	Prism, colourless
V = 665.96 (7) Å^3	0.3 × 0.2 × 0.2 mm

Data collection

Agilent Xcalibur Eos diffractometer	4020 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3638 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 16.1544 pixels mm^-1	θmax = 28.3°, θmin = 3.0°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −8→9
Tmin = 0.893, Tmax = 1.000	l = −15→18
5170 measured reflections

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)] = 0.034	w = 1/[σ^2(Fo^2) + (0.017P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.063	(Δ/σ)max = 0.001
S = 0.98	Δρmax = 0.97 e Å^−3
4020 reflections	Δρmin = −0.80 e Å^−3
289 parameters	Absolute structure: Flack x determined using 1081 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
159 restraints	Absolute structure parameter: 0.05 (4)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.25113 (10)	0.31119 (10)	0.54603 (7)	0.01932 (18)
I2	0.40750 (9)	0.28792 (8)	0.22606 (6)	0.0184 (2)
I3	0.31005 (12)	0.24863 (11)	0.04134 (7)	0.01617 (16)
I4	0.20290 (9)	0.21986 (8)	−0.14134 (5)	0.0183 (2)
N1A	0.7105 (13)	0.7488 (13)	0.7640 (8)	0.012 (2)
C2A	0.6152 (17)	0.6253 (16)	0.7721 (10)	0.011 (3)
O2A	0.5700 (11)	0.6055 (11)	0.6953 (7)	0.018 (2)
C3A	0.5736 (16)	0.5396 (16)	0.8679 (9)	0.014 (3)
H3A	0.5187	0.4464	0.8763	0.017*
C4A	0.6096 (16)	0.5860 (16)	0.9489 (9)	0.016 (3)
H4A	0.5746	0.5296	1.0131	0.019*
C5A	0.6969 (18)	0.7148 (18)	0.9385 (10)	0.016 (3)
H5A	0.7228	0.7467	0.9951	0.019*
C6A	0.7451 (16)	0.7948 (16)	0.8467 (9)	0.010 (2)
C7A	0.8561 (16)	0.9249 (16)	0.8280 (9)	0.013 (3)
H7A	0.8160	0.9986	0.8889	0.016*
C8A	0.7949 (16)	1.0823 (15)	0.7409 (9)	0.016 (2)
H8A1	0.6434	1.1704	0.7527	0.019*
H8A2	0.8643	1.1687	0.7324	0.019*
C9A	0.8613 (16)	0.9682 (16)	0.6492 (9)	0.014 (3)
H9A	0.8215	1.0693	0.5910	0.017*
C10A	0.7459 (17)	0.8416 (16)	0.6635 (9)	0.013 (3)
H10A	0.6098	0.9297	0.6435	0.015*
H10B	0.8245	0.7316	0.6173	0.015*
C11A	1.0948 (15)	0.8362 (15)	0.6287 (8)	0.013 (2)
H11A	1.1331	0.7585	0.5702	0.015*
H11B	1.1629	0.9250	0.6120	0.015*
N12A	1.1732 (13)	0.6910 (12)	0.7150 (7)	0.012 (2)
H12A	1.1355	0.5801	0.7204	0.014*
H12B	1.3260	0.6297	0.7025	0.014*
C13A	1.0886 (16)	0.7896 (16)	0.8113 (9)	0.014 (2)
H13A	1.1577	0.8722	0.8129	0.017*
H13B	1.1221	0.6826	0.8666	0.017*
N1B	0.8607 (13)	0.8059 (12)	0.3256 (7)	0.008 (2)
C2B	0.9841 (18)	0.9003 (17)	0.3171 (10)	0.014 (3)
O2B	0.9920 (11)	0.9613 (11)	0.3937 (6)	0.0157 (19)
C3B	1.0955 (16)	0.9170 (16)	0.2206 (9)	0.014 (3)
H3B	1.1890	0.9722	0.2118	0.017*
C4B	1.0725 (16)	0.8573 (16)	0.1417 (9)	0.015 (3)
H4B	1.1449	0.8748	0.0773	0.018*
C5B	0.9378 (17)	0.7666 (17)	0.1547 (10)	0.013 (3)
H5B	0.9203	0.7226	0.0994	0.016*
C6B	0.8369 (16)	0.7450 (15)	0.2469 (9)	0.012 (2)
C7B	0.6999 (17)	0.6410 (16)	0.2641 (9)	0.016 (3)
H7B	0.6405	0.6687	0.2028	0.019*
C8B	0.5210 (16)	0.7265 (16)	0.3511 (9)	0.016 (2)
H8B1	0.4309	0.6605	0.3609	0.019*
H8B2	0.4368	0.8748	0.3383	0.019*
C9B	0.6197 (17)	0.6814 (16)	0.4436 (9)	0.013 (3)
H9B	0.5055	0.7359	0.5020	0.015*
C10B	0.7489 (18)	0.7935 (17)	0.4279 (9)	0.016 (3)
H10C	0.6564	0.9335	0.4484	0.019*
H10D	0.8512	0.7256	0.4726	0.019*
C11B	0.7407 (16)	0.4512 (15)	0.4641 (9)	0.018 (3)
H11C	0.8050	0.4222	0.5230	0.022*
H11D	0.6440	0.3915	0.4794	0.022*
N12B	0.9039 (13)	0.3545 (12)	0.3781 (7)	0.012 (2)
H12C	0.9662	0.2051	0.3917	0.014*
H12D	1.0141	0.3949	0.3711	0.014*
C13B	0.8271 (15)	0.4097 (15)	0.2819 (9)	0.014 (2)
H13C	0.7402	0.3437	0.2829	0.016*
H13D	0.9464	0.3585	0.2265	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0163 (4)	0.0155 (4)	0.0280 (5)	−0.0069 (3)	−0.0073 (3)	−0.0028 (3)
I2	0.0166 (4)	0.0171 (4)	0.0226 (6)	−0.0080 (4)	−0.0069 (4)	0.0013 (4)
I3	0.0173 (3)	0.0144 (3)	0.0171 (4)	−0.0099 (3)	0.0024 (3)	−0.0016 (3)
I4	0.0179 (4)	0.0154 (4)	0.0224 (6)	−0.0075 (3)	−0.0031 (3)	−0.0050 (4)
N1A	0.009 (3)	0.014 (3)	0.011 (4)	−0.004 (3)	−0.002 (3)	0.000 (3)
C2A	0.011 (4)	0.010 (4)	0.011 (4)	−0.004 (3)	−0.002 (3)	0.000 (3)
O2A	0.016 (4)	0.023 (4)	0.019 (6)	−0.011 (4)	−0.002 (4)	−0.004 (4)
C3A	0.014 (4)	0.013 (4)	0.014 (4)	−0.008 (3)	0.001 (3)	0.003 (3)
C4A	0.014 (4)	0.016 (4)	0.012 (4)	−0.005 (3)	0.000 (3)	0.001 (3)
C5A	0.015 (4)	0.018 (4)	0.013 (4)	−0.006 (3)	−0.003 (3)	−0.003 (3)
C6A	0.009 (4)	0.011 (4)	0.008 (4)	−0.002 (3)	−0.004 (3)	0.000 (3)
C7A	0.012 (4)	0.015 (4)	0.016 (4)	−0.008 (3)	−0.001 (3)	−0.004 (3)
C8A	0.014 (4)	0.015 (4)	0.021 (4)	−0.009 (3)	−0.001 (3)	−0.002 (3)
C9A	0.013 (4)	0.016 (4)	0.015 (4)	−0.009 (3)	−0.004 (3)	0.002 (3)
C10A	0.014 (4)	0.014 (4)	0.011 (4)	−0.007 (3)	−0.001 (3)	−0.001 (3)
C11A	0.012 (4)	0.013 (4)	0.014 (4)	−0.007 (3)	−0.003 (3)	0.000 (3)
N12A	0.013 (3)	0.010 (3)	0.015 (4)	−0.007 (3)	−0.003 (3)	−0.003 (3)
C13A	0.013 (4)	0.017 (4)	0.017 (4)	−0.009 (3)	−0.004 (3)	−0.003 (3)
N1B	0.009 (3)	0.006 (3)	0.008 (3)	−0.005 (3)	−0.002 (3)	0.002 (3)
C2B	0.015 (4)	0.012 (4)	0.015 (4)	−0.004 (3)	−0.005 (3)	0.000 (3)
O2B	0.022 (4)	0.018 (4)	0.016 (5)	−0.015 (4)	−0.010 (4)	0.004 (4)
C3B	0.011 (4)	0.017 (4)	0.012 (4)	−0.008 (3)	0.001 (3)	0.001 (3)
C4B	0.016 (4)	0.014 (4)	0.013 (4)	−0.007 (3)	−0.002 (3)	0.002 (3)
C5B	0.015 (4)	0.013 (4)	0.012 (4)	−0.005 (3)	−0.002 (3)	−0.003 (3)
C6B	0.012 (4)	0.009 (4)	0.011 (4)	−0.004 (3)	−0.001 (3)	0.001 (3)
C7B	0.017 (4)	0.018 (4)	0.016 (4)	−0.008 (3)	−0.008 (3)	−0.002 (3)
C8B	0.016 (4)	0.015 (4)	0.020 (4)	−0.009 (3)	−0.005 (3)	−0.001 (3)
C9B	0.012 (4)	0.014 (4)	0.011 (4)	−0.006 (3)	−0.001 (3)	0.000 (3)
C10B	0.016 (4)	0.017 (4)	0.013 (4)	−0.006 (3)	−0.003 (3)	−0.001 (3)
C11B	0.018 (4)	0.019 (4)	0.017 (4)	−0.009 (3)	−0.002 (3)	0.000 (3)
N12B	0.013 (3)	0.013 (3)	0.013 (4)	−0.008 (3)	−0.003 (3)	0.001 (3)
C13B	0.016 (4)	0.013 (4)	0.017 (4)	−0.010 (3)	−0.005 (3)	−0.001 (3)

Geometric parameters (Å, º)

I2—I3	2.9360 (12)	C13A—H13B	0.9900
I3—I4	2.9174 (12)	N1B—C6B	1.340 (14)
N1A—C6A	1.373 (14)	N1B—C2B	1.390 (14)
N1A—C2A	1.399 (15)	N1B—C10B	1.476 (14)
N1A—C10A	1.468 (14)	C2B—O2B	1.258 (15)
C2A—O2A	1.248 (14)	C2B—C3B	1.416 (17)
C2A—C3A	1.403 (16)	C3B—C4B	1.334 (16)
C3A—C4A	1.360 (15)	C3B—H3B	0.9500
C3A—H3A	0.9500	C4B—C5B	1.434 (15)
C4A—C5A	1.382 (15)	C4B—H4B	0.9500
C4A—H4A	0.9500	C5B—C6B	1.345 (16)
C5A—C6A	1.352 (17)	C5B—H5B	0.9500
C5A—H5A	0.9500	C6B—C7B	1.523 (15)
C6A—C7A	1.521 (15)	C7B—C8B	1.526 (15)
C7A—C13A	1.520 (14)	C7B—C13B	1.537 (14)
C7A—C8A	1.521 (16)	C7B—H7B	1.0000
C7A—H7A	1.0000	C8B—C9B	1.545 (16)
C8A—C9A	1.510 (15)	C8B—H8B1	0.9900
C8A—H8A1	0.9900	C8B—H8B2	0.9900
C8A—H8A2	0.9900	C9B—C10B	1.525 (15)
C9A—C11A	1.522 (14)	C9B—C11B	1.530 (14)
C9A—C10A	1.532 (14)	C9B—H9B	1.0000
C9A—H9A	1.0000	C10B—H10C	0.9900
C10A—H10A	0.9900	C10B—H10D	0.9900
C10A—H10B	0.9900	C11B—N12B	1.482 (13)
C11A—N12A	1.495 (13)	C11B—H11C	0.9900
C11A—H11A	0.9900	C11B—H11D	0.9900
C11A—H11B	0.9900	N12B—C13B	1.496 (13)
N12A—C13A	1.494 (13)	N12B—H12C	0.9900
N12A—H12A	0.9900	N12B—H12D	0.9900
N12A—H12B	0.9900	C13B—H13C	0.9900
C13A—H13A	0.9900	C13B—H13D	0.9900
I4—I3—I2	178.45 (3)	C6B—N1B—C2B	122.6 (10)
C6A—N1A—C2A	121.2 (11)	C6B—N1B—C10B	124.0 (9)
C6A—N1A—C10A	123.7 (10)	C2B—N1B—C10B	113.3 (9)
C2A—N1A—C10A	114.7 (10)	O2B—C2B—N1B	119.0 (11)
O2A—C2A—N1A	118.0 (11)	O2B—C2B—C3B	124.9 (12)
O2A—C2A—C3A	126.0 (11)	N1B—C2B—C3B	116.1 (11)
N1A—C2A—C3A	115.9 (11)	C4B—C3B—C2B	121.7 (11)
C4A—C3A—C2A	121.9 (11)	C4B—C3B—H3B	119.2
C4A—C3A—H3A	119.1	C2B—C3B—H3B	119.2
C2A—C3A—H3A	119.1	C3B—C4B—C5B	119.6 (11)
C3A—C4A—C5A	120.4 (11)	C3B—C4B—H4B	120.2
C3A—C4A—H4A	119.8	C5B—C4B—H4B	120.2
C5A—C4A—H4A	119.8	C6B—C5B—C4B	118.6 (12)
C6A—C5A—C4A	119.2 (12)	C6B—C5B—H5B	120.7
C6A—C5A—H5A	120.4	C4B—C5B—H5B	120.7
C4A—C5A—H5A	120.4	N1B—C6B—C5B	121.3 (11)
C5A—C6A—N1A	121.2 (11)	N1B—C6B—C7B	118.6 (10)
C5A—C6A—C7A	122.3 (11)	C5B—C6B—C7B	120.1 (11)
N1A—C6A—C7A	116.2 (10)	C6B—C7B—C8B	110.9 (9)
C13A—C7A—C8A	110.9 (10)	C6B—C7B—C13B	110.8 (9)
C13A—C7A—C6A	109.8 (8)	C8B—C7B—C13B	110.7 (10)
C8A—C7A—C6A	112.0 (9)	C6B—C7B—H7B	108.1
C13A—C7A—H7A	108.0	C8B—C7B—H7B	108.1
C8A—C7A—H7A	108.0	C13B—C7B—H7B	108.1
C6A—C7A—H7A	108.0	C7B—C8B—C9B	106.3 (9)
C9A—C8A—C7A	107.2 (9)	C7B—C8B—H8B1	110.5
C9A—C8A—H8A1	110.3	C9B—C8B—H8B1	110.5
C7A—C8A—H8A1	110.3	C7B—C8B—H8B2	110.5
C9A—C8A—H8A2	110.3	C9B—C8B—H8B2	110.5
C7A—C8A—H8A2	110.3	H8B1—C8B—H8B2	108.7
H8A1—C8A—H8A2	108.5	C10B—C9B—C11B	114.2 (9)
C8A—C9A—C11A	110.8 (9)	C10B—C9B—C8B	109.0 (9)
C8A—C9A—C10A	108.9 (9)	C11B—C9B—C8B	109.2 (9)
C11A—C9A—C10A	111.6 (9)	C10B—C9B—H9B	108.1
C8A—C9A—H9A	108.5	C11B—C9B—H9B	108.1
C11A—C9A—H9A	108.5	C8B—C9B—H9B	108.1
C10A—C9A—H9A	108.5	N1B—C10B—C9B	116.0 (10)
N1A—C10A—C9A	116.8 (10)	N1B—C10B—H10C	108.3
N1A—C10A—H10A	108.1	C9B—C10B—H10C	108.3
C9A—C10A—H10A	108.1	N1B—C10B—H10D	108.3
N1A—C10A—H10B	108.1	C9B—C10B—H10D	108.3
C9A—C10A—H10B	108.1	H10C—C10B—H10D	107.4
H10A—C10A—H10B	107.3	N12B—C11B—C9B	111.9 (9)
N12A—C11A—C9A	112.9 (9)	N12B—C11B—H11C	109.2
N12A—C11A—H11A	109.0	C9B—C11B—H11C	109.2
C9A—C11A—H11A	109.0	N12B—C11B—H11D	109.2
N12A—C11A—H11B	109.0	C9B—C11B—H11D	109.2
C9A—C11A—H11B	109.0	H11C—C11B—H11D	107.9
H11A—C11A—H11B	107.8	C11B—N12B—C13B	113.7 (8)
C13A—N12A—C11A	112.9 (8)	C11B—N12B—H12C	108.8
C13A—N12A—H12A	109.0	C13B—N12B—H12C	108.8
C11A—N12A—H12A	109.0	C11B—N12B—H12D	108.8
C13A—N12A—H12B	109.0	C13B—N12B—H12D	108.8
C11A—N12A—H12B	109.0	H12C—N12B—H12D	107.7
H12A—N12A—H12B	107.8	N12B—C13B—C7B	111.4 (8)
N12A—C13A—C7A	113.5 (9)	N12B—C13B—H13C	109.3
N12A—C13A—H13A	108.9	C7B—C13B—H13C	109.3
C7A—C13A—H13A	108.9	N12B—C13B—H13D	109.3
N12A—C13A—H13B	108.9	C7B—C13B—H13D	109.3
C7A—C13A—H13B	108.9	H13C—C13B—H13D	108.0
H13A—C13A—H13B	107.7
C6A—N1A—C2A—O2A	173.1 (9)	C6B—N1B—C2B—O2B	176.9 (10)
C10A—N1A—C2A—O2A	0.0 (14)	C10B—N1B—C2B—O2B	1.0 (13)
C6A—N1A—C2A—C3A	−5.0 (14)	C6B—N1B—C2B—C3B	−4.0 (14)
C10A—N1A—C2A—C3A	−178.1 (9)	C10B—N1B—C2B—C3B	−180.0 (10)
O2A—C2A—C3A—C4A	−173.2 (10)	O2B—C2B—C3B—C4B	−176.9 (10)
N1A—C2A—C3A—C4A	4.8 (15)	N1B—C2B—C3B—C4B	4.1 (16)
C2A—C3A—C4A—C5A	−2.5 (16)	C2B—C3B—C4B—C5B	−2.4 (16)
C3A—C4A—C5A—C6A	0.3 (16)	C3B—C4B—C5B—C6B	0.3 (16)
C4A—C5A—C6A—N1A	−0.6 (17)	C2B—N1B—C6B—C5B	2.2 (15)
C4A—C5A—C6A—C7A	−175.3 (10)	C10B—N1B—C6B—C5B	177.7 (10)
C2A—N1A—C6A—C5A	3.1 (15)	C2B—N1B—C6B—C7B	179.4 (9)
C10A—N1A—C6A—C5A	175.6 (10)	C10B—N1B—C6B—C7B	−5.1 (14)
C2A—N1A—C6A—C7A	178.1 (9)	C4B—C5B—C6B—N1B	−0.2 (16)
C10A—N1A—C6A—C7A	−9.4 (13)	C4B—C5B—C6B—C7B	−177.3 (9)
C5A—C6A—C7A—C13A	87.0 (13)	N1B—C6B—C7B—C8B	33.2 (14)
N1A—C6A—C7A—C13A	−88.0 (11)	C5B—C6B—C7B—C8B	−149.6 (11)
C5A—C6A—C7A—C8A	−149.4 (11)	N1B—C6B—C7B—C13B	−90.1 (11)
N1A—C6A—C7A—C8A	35.7 (12)	C5B—C6B—C7B—C13B	87.1 (13)
C13A—C7A—C8A—C9A	60.5 (11)	C6B—C7B—C8B—C9B	−61.4 (11)
C6A—C7A—C8A—C9A	−62.5 (11)	C13B—C7B—C8B—C9B	62.0 (11)
C7A—C8A—C9A—C11A	−61.4 (11)	C7B—C8B—C9B—C10B	62.8 (11)
C7A—C8A—C9A—C10A	61.7 (11)	C7B—C8B—C9B—C11B	−62.6 (11)
C6A—N1A—C10A—C9A	10.6 (14)	C6B—N1B—C10B—C9B	7.3 (14)
C2A—N1A—C10A—C9A	−176.5 (9)	C2B—N1B—C10B—C9B	−176.8 (10)
C8A—C9A—C10A—N1A	−37.0 (13)	C11B—C9B—C10B—N1B	85.9 (12)
C11A—C9A—C10A—N1A	85.6 (12)	C8B—C9B—C10B—N1B	−36.6 (12)
C8A—C9A—C11A—N12A	56.1 (12)	C10B—C9B—C11B—N12B	−64.0 (12)
C10A—C9A—C11A—N12A	−65.4 (12)	C8B—C9B—C11B—N12B	58.4 (12)
C9A—C11A—N12A—C13A	−47.6 (11)	C9B—C11B—N12B—C13B	−51.9 (11)
C11A—N12A—C13A—C7A	46.9 (11)	C11B—N12B—C13B—C7B	50.0 (11)
C8A—C7A—C13A—N12A	−54.3 (11)	C6B—C7B—C13B—N12B	67.4 (12)
C6A—C7A—C13A—N12A	70.0 (12)	C8B—C7B—C13B—N12B	−56.0 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12A—H12B···O2A^i	0.99	1.73	2.680 (11)	159
N12A—H12A···I4^ii	0.99	2.93	3.679 (8)	133
N12B—H12C···O2B^iii	0.99	1.75	2.686 (11)	157
N12B—H12D···I2^i	0.99	2.97	3.694 (8)	131

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

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium chloride monohydrate (5)

Crystal data

C11H15N2O^+·Cl^−·H2O	F(000) = 260
Mr = 244.71	Dx = 1.404 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.6327 (2) Å	Cell parameters from 6830 reflections
b = 10.4510 (2) Å	θ = 3.3–28.8°
c = 7.6553 (2) Å	µ = 0.32 mm^−1
β = 108.559 (3)°	T = 100 K
V = 578.90 (3) Å^3	Prism, colourless
Z = 2	0.3 × 0.2 × 0.15 mm

Data collection

Agilent Xcalibur Eos diffractometer	2796 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2653 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 16.1544 pixels mm^-1	θmax = 29.1°, θmin = 3.3°
ω scan	h = −9→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −14→13
Tmin = 0.948, Tmax = 1.000	l = −10→10
12838 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0399P)^2 + 0.0651P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.30 e Å^−3
2796 reflections	Δρmin = −0.18 e Å^−3
213 parameters	Absolute structure: Flack x determined using 1146 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.05 (2)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
N1	0.9528 (2)	0.40164 (16)	0.3411 (2)	0.0108 (3)
C2	1.0704 (3)	0.37643 (19)	0.2388 (3)	0.0123 (4)
O2	1.1753 (2)	0.28052 (13)	0.2816 (2)	0.0152 (3)
C3	1.0639 (3)	0.4630 (2)	0.0941 (3)	0.0150 (4)
H3	1.139 (4)	0.447 (3)	0.020 (4)	0.021 (7)*
C4	0.9509 (3)	0.5669 (2)	0.0613 (3)	0.0158 (4)
H4	0.945 (4)	0.623 (3)	−0.035 (4)	0.017 (6)*
C5	0.8352 (3)	0.5890 (2)	0.1691 (3)	0.0139 (4)
H5	0.754 (4)	0.661 (3)	0.148 (4)	0.022 (7)*
C6	0.8389 (3)	0.50680 (18)	0.3083 (3)	0.0119 (4)
C7	0.7184 (3)	0.52863 (19)	0.4289 (3)	0.0128 (4)
H7	0.707 (4)	0.617 (3)	0.437 (4)	0.019 (7)*
C8	0.8061 (3)	0.4710 (2)	0.6193 (3)	0.0152 (4)
H8A	0.915 (4)	0.514 (2)	0.674 (4)	0.016 (6)*
H8B	0.737 (4)	0.487 (3)	0.704 (4)	0.022 (7)*
C9	0.8266 (3)	0.3288 (2)	0.5917 (3)	0.0139 (4)
H9	0.876 (4)	0.286 (2)	0.710 (4)	0.016 (6)*
C10	0.9671 (3)	0.3082 (2)	0.4912 (3)	0.0146 (4)
H10A	1.096 (4)	0.320 (3)	0.581 (4)	0.024 (7)*
H10B	0.964 (3)	0.220 (2)	0.440 (3)	0.006 (5)*
C11	0.6395 (3)	0.2664 (2)	0.4980 (3)	0.0149 (4)
H11A	0.653 (4)	0.176 (3)	0.468 (4)	0.023 (8)*
H11B	0.566 (3)	0.271 (2)	0.581 (3)	0.011 (6)*
N12	0.5325 (3)	0.33156 (17)	0.3224 (2)	0.0128 (4)
H12A	0.419 (4)	0.308 (2)	0.293 (3)	0.013 (6)*
H12B	0.574 (4)	0.309 (2)	0.227 (3)	0.012 (6)*
C13	0.5253 (3)	0.4736 (2)	0.3415 (3)	0.0140 (4)
H13A	0.455 (4)	0.482 (2)	0.420 (3)	0.011 (6)*
H13B	0.471 (4)	0.508 (3)	0.220 (4)	0.022 (7)*
Cl1	0.37566 (8)	0.74989 (5)	0.02606 (7)	0.02257 (15)
O1W	0.3586 (3)	0.4916 (2)	0.7708 (3)	0.0399 (5)
H1W2	0.355 (6)	0.565 (4)	0.850 (6)	0.072 (13)*
H1W1	0.425 (5)	0.432 (4)	0.833 (5)	0.050 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0105 (8)	0.0108 (8)	0.0113 (8)	−0.0002 (6)	0.0038 (6)	0.0005 (6)
C2	0.0101 (9)	0.0136 (9)	0.0130 (9)	−0.0032 (7)	0.0034 (7)	−0.0028 (7)
O2	0.0120 (7)	0.0152 (8)	0.0194 (7)	0.0007 (5)	0.0065 (6)	0.0003 (5)
C3	0.0136 (10)	0.0194 (10)	0.0131 (10)	−0.0037 (8)	0.0058 (8)	−0.0025 (8)
C4	0.0196 (11)	0.0161 (10)	0.0104 (9)	−0.0050 (8)	0.0030 (8)	0.0025 (8)
C5	0.0143 (10)	0.0119 (9)	0.0133 (10)	−0.0017 (8)	0.0012 (8)	−0.0002 (8)
C6	0.0103 (9)	0.0119 (9)	0.0122 (9)	−0.0018 (7)	0.0018 (8)	−0.0031 (7)
C7	0.0140 (10)	0.0090 (9)	0.0156 (10)	−0.0001 (8)	0.0050 (8)	−0.0015 (7)
C8	0.0158 (10)	0.0176 (10)	0.0126 (10)	−0.0017 (9)	0.0048 (8)	−0.0033 (8)
C9	0.0139 (10)	0.0169 (10)	0.0122 (9)	0.0017 (8)	0.0058 (8)	0.0034 (8)
C10	0.0139 (11)	0.0151 (10)	0.0157 (10)	0.0028 (8)	0.0060 (8)	0.0051 (8)
C11	0.0156 (10)	0.0152 (12)	0.0161 (9)	0.0013 (8)	0.0083 (8)	0.0021 (8)
N12	0.0118 (9)	0.0137 (8)	0.0139 (9)	−0.0017 (7)	0.0055 (7)	−0.0018 (7)
C13	0.0136 (10)	0.0117 (10)	0.0176 (10)	0.0011 (8)	0.0063 (8)	−0.0006 (8)
Cl1	0.0256 (3)	0.0258 (3)	0.0205 (3)	0.0091 (2)	0.0131 (2)	0.0100 (2)
O1W	0.0459 (13)	0.0369 (12)	0.0328 (11)	0.0006 (10)	0.0067 (10)	0.0002 (9)

Geometric parameters (Å, º)

N1—C6	1.374 (3)	C8—H8B	0.97 (3)
N1—C2	1.392 (3)	C9—C10	1.521 (3)
N1—C10	1.485 (3)	C9—C11	1.526 (3)
C2—O2	1.259 (3)	C9—H9	0.97 (3)
C2—C3	1.419 (3)	C10—H10A	1.01 (3)
C3—C4	1.359 (3)	C10—H10B	1.00 (2)
C3—H3	0.94 (3)	C11—N12	1.496 (3)
C4—C5	1.407 (3)	C11—H11A	0.98 (3)
C4—H4	0.93 (3)	C11—H11B	0.98 (2)
C5—C6	1.362 (3)	N12—C13	1.494 (3)
C5—H5	0.95 (3)	N12—H12A	0.86 (3)
C6—C7	1.513 (3)	N12—H12B	0.92 (3)
C7—C8	1.521 (3)	C13—H13A	0.92 (2)
C7—C13	1.524 (3)	C13—H13B	0.96 (3)
C7—H7	0.93 (3)	O1W—H1W2	0.98 (4)
C8—C9	1.516 (3)	O1W—H1W1	0.85 (4)
C8—H8A	0.92 (3)
C6—N1—C2	122.20 (17)	C8—C9—C11	111.21 (18)
C6—N1—C10	123.58 (16)	C10—C9—C11	114.01 (18)
C2—N1—C10	114.18 (15)	C8—C9—H9	110.2 (15)
O2—C2—N1	118.35 (17)	C10—C9—H9	106.3 (16)
O2—C2—C3	124.90 (19)	C11—C9—H9	105.7 (15)
N1—C2—C3	116.75 (18)	N1—C10—C9	114.12 (17)
C4—C3—C2	121.1 (2)	N1—C10—H10A	105.4 (16)
C4—C3—H3	120.0 (18)	C9—C10—H10A	109.1 (15)
C2—C3—H3	118.9 (18)	N1—C10—H10B	108.6 (13)
C3—C4—C5	120.18 (19)	C9—C10—H10B	113.2 (14)
C3—C4—H4	120.9 (18)	H10A—C10—H10B	106 (2)
C5—C4—H4	118.9 (17)	N12—C11—C9	112.90 (17)
C6—C5—C4	119.7 (2)	N12—C11—H11A	107.1 (16)
C6—C5—H5	118.7 (17)	C9—C11—H11A	111.6 (18)
C4—C5—H5	121.6 (17)	N12—C11—H11B	107.4 (14)
C5—C6—N1	120.09 (19)	C9—C11—H11B	108.6 (14)
C5—C6—C7	121.14 (18)	H11A—C11—H11B	109 (2)
N1—C6—C7	118.77 (17)	C13—N12—C11	113.00 (17)
C6—C7—C8	110.94 (17)	C13—N12—H12A	104.2 (17)
C6—C7—C13	111.43 (17)	C11—N12—H12A	108.9 (17)
C8—C7—C13	109.90 (18)	C13—N12—H12B	111.6 (15)
C6—C7—H7	106.0 (17)	C11—N12—H12B	111.7 (16)
C8—C7—H7	110.6 (17)	H12A—N12—H12B	107 (2)
C13—C7—H7	107.8 (17)	N12—C13—C7	110.93 (18)
C9—C8—C7	106.73 (17)	N12—C13—H13A	101.7 (16)
C9—C8—H8A	115.3 (16)	C7—C13—H13A	111.0 (15)
C7—C8—H8A	107.3 (16)	N12—C13—H13B	107.2 (17)
C9—C8—H8B	111.3 (16)	C7—C13—H13B	110.1 (18)
C7—C8—H8B	113.9 (17)	H13A—C13—H13B	116 (2)
H8A—C8—H8B	102 (2)	H1W2—O1W—H1W1	111 (3)
C8—C9—C10	109.28 (18)
C6—N1—C2—O2	177.52 (18)	C5—C6—C7—C13	84.9 (2)
C10—N1—C2—O2	−0.4 (3)	N1—C6—C7—C13	−94.9 (2)
C6—N1—C2—C3	−1.7 (3)	C6—C7—C8—C9	−60.1 (2)
C10—N1—C2—C3	−179.60 (18)	C13—C7—C8—C9	63.6 (2)
O2—C2—C3—C4	−177.6 (2)	C7—C8—C9—C10	66.7 (2)
N1—C2—C3—C4	1.6 (3)	C7—C8—C9—C11	−60.1 (2)
C2—C3—C4—C5	−1.2 (3)	C6—N1—C10—C9	7.4 (3)
C3—C4—C5—C6	1.0 (3)	C2—N1—C10—C9	−174.76 (18)
C4—C5—C6—N1	−1.1 (3)	C8—C9—C10—N1	−40.3 (2)
C4—C5—C6—C7	179.09 (18)	C11—C9—C10—N1	84.8 (2)
C2—N1—C6—C5	1.5 (3)	C8—C9—C11—N12	53.4 (2)
C10—N1—C6—C5	179.21 (19)	C10—C9—C11—N12	−70.7 (2)
C2—N1—C6—C7	−178.64 (17)	C9—C11—N12—C13	−48.3 (2)
C10—N1—C6—C7	−1.0 (3)	C11—N12—C13—C7	51.3 (2)
C5—C6—C7—C8	−152.29 (19)	C6—C7—C13—N12	63.5 (2)
N1—C6—C7—C8	27.9 (2)	C8—C7—C13—N12	−59.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···O2^i	0.86 (3)	1.86 (3)	2.697 (2)	165 (2)
N12—H12B···Cl1^ii	0.92 (3)	2.18 (3)	3.0863 (19)	170 (2)
O1W—H1W2···Cl1^iii	0.98 (4)	2.33 (5)	3.311 (2)	173 (4)
O1W—H1W1···Cl1^iv	0.85 (4)	2.46 (4)	3.302 (2)	172 (3)

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

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium iodide monohydrate (6)

Crystal data

C11H15N2O^+·I^−·H2O	F(000) = 332
Mr = 336.16	Dx = 1.809 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.7268 (4) Å	Cell parameters from 1275 reflections
b = 10.4304 (4) Å	θ = 3.3–27.8°
c = 8.0655 (4) Å	µ = 2.58 mm^−1
β = 108.341 (5)°	T = 100 K
V = 617.01 (5) Å^3	Prism, colourless
Z = 2	0.25 × 0.1 × 0.05 mm

Data collection

Agilent Xcalibur Eos diffractometer	2262 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2028 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.1544 pixels mm^-1	θmax = 28.2°, θmin = 3.2°
ω scan	h = −10→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→13
Tmin = 0.779, Tmax = 1.000	l = −10→10
3889 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 1.1015P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 3.39 e Å^−3
2262 reflections	Δρmin = −1.23 e Å^−3
145 parameters	Absolute structure: Flack x determined using 755 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
79 restraints	Absolute structure parameter: 0.04 (2)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.60557 (7)	−0.05810 (8)	0.20392 (7)	0.02348 (18)
N1	0.9556 (10)	0.4007 (6)	0.3317 (9)	0.0110 (14)
C2	1.0742 (10)	0.3757 (8)	0.2374 (11)	0.0115 (17)
O2	1.1804 (8)	0.2812 (5)	0.2774 (8)	0.0140 (12)
C3	1.0664 (10)	0.4578 (12)	0.0992 (10)	0.021 (2)
H3	1.1401	0.4405	0.0271	0.026*
C4	0.9518 (11)	0.5656 (8)	0.0642 (11)	0.0143 (17)
H4	0.9484	0.6216	−0.0296	0.017*
C5	0.8423 (11)	0.5889 (8)	0.1711 (11)	0.0131 (17)
H5	0.7661	0.6625	0.1516	0.016*
C6	0.8454 (11)	0.5060 (8)	0.3024 (10)	0.0077 (15)
C7	0.7273 (10)	0.5294 (8)	0.4177 (10)	0.0096 (16)
H7	0.7182	0.6241	0.4330	0.012*
C8	0.8175 (11)	0.4686 (8)	0.6005 (11)	0.017 (2)
H8A	0.9408	0.5047	0.6555	0.021*
H8B	0.7429	0.4851	0.6780	0.021*
C9	0.8288 (12)	0.3245 (8)	0.5687 (12)	0.0163 (18)
H9	0.8812	0.2826	0.6853	0.020*
C10	0.9627 (11)	0.3030 (8)	0.4674 (11)	0.0119 (16)
H10A	1.0877	0.3013	0.5512	0.014*
H10B	0.9385	0.2178	0.4107	0.014*
C11	0.6400 (11)	0.2684 (8)	0.4849 (11)	0.0151 (17)
H11A	0.6518	0.1762	0.4618	0.018*
H11B	0.5694	0.2758	0.5678	0.018*
N12	0.5374 (9)	0.3337 (7)	0.3175 (9)	0.0114 (15)
H12A	0.4103	0.3017	0.2781	0.014*
H12B	0.5938	0.3112	0.2269	0.014*
C13	0.5354 (10)	0.4766 (7)	0.3351 (11)	0.0095 (17)
H13A	0.4587	0.5004	0.4082	0.011*
H13B	0.4809	0.5155	0.2183	0.011*
O1W	0.7005 (9)	0.2387 (7)	0.0731 (9)	0.0292 (16)
H1W1	0.6324	0.2696	−0.0229	0.035*
H1W2	0.6685	0.1605	0.0721	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0241 (3)	0.0269 (3)	0.0251 (3)	0.0095 (4)	0.0158 (2)	0.0078 (4)
N1	0.014 (3)	0.010 (3)	0.009 (3)	−0.003 (2)	0.004 (2)	−0.002 (2)
C2	0.007 (3)	0.012 (4)	0.014 (4)	−0.004 (3)	0.001 (3)	−0.005 (3)
O2	0.011 (3)	0.011 (3)	0.022 (3)	0.002 (2)	0.008 (3)	−0.001 (2)
C3	0.018 (3)	0.030 (5)	0.017 (3)	0.005 (4)	0.008 (3)	0.010 (4)
C4	0.014 (4)	0.014 (4)	0.015 (4)	−0.006 (3)	0.004 (3)	−0.001 (3)
C5	0.009 (3)	0.010 (3)	0.018 (4)	0.001 (3)	0.001 (3)	−0.001 (3)
C6	0.004 (3)	0.007 (3)	0.010 (3)	−0.002 (2)	0.001 (2)	−0.003 (2)
C7	0.013 (4)	0.007 (3)	0.008 (3)	−0.005 (3)	0.004 (3)	0.000 (3)
C8	0.014 (3)	0.024 (4)	0.016 (3)	−0.008 (3)	0.007 (2)	−0.014 (3)
C9	0.017 (4)	0.015 (4)	0.020 (4)	0.008 (3)	0.010 (3)	0.006 (3)
C10	0.012 (3)	0.008 (3)	0.014 (4)	0.004 (3)	0.003 (3)	0.005 (3)
C11	0.018 (4)	0.015 (4)	0.018 (4)	0.000 (3)	0.012 (3)	0.004 (3)
N12	0.012 (3)	0.011 (3)	0.014 (3)	0.000 (3)	0.007 (3)	−0.002 (3)
C13	0.007 (3)	0.007 (4)	0.014 (3)	0.000 (2)	0.003 (3)	−0.001 (3)
O1W	0.030 (4)	0.028 (4)	0.030 (4)	0.000 (3)	0.011 (3)	0.000 (3)

Geometric parameters (Å, º)

N1—C6	1.365 (10)	C8—H8B	0.9900
N1—C2	1.387 (10)	C9—C11	1.518 (13)
N1—C10	1.483 (10)	C9—C10	1.523 (10)
C2—O2	1.258 (10)	C9—H9	1.0000
C2—C3	1.392 (12)	C10—H10A	0.9900
C3—C4	1.404 (14)	C10—H10B	0.9900
C3—H3	0.9500	C11—N12	1.497 (11)
C4—C5	1.406 (11)	C11—H11A	0.9900
C4—H4	0.9500	C11—H11B	0.9900
C5—C6	1.362 (11)	N12—C13	1.498 (11)
C5—H5	0.9500	N12—H12A	0.9900
C6—C7	1.513 (10)	N12—H12B	0.9900
C7—C13	1.524 (11)	C13—H13A	0.9900
C7—C8	1.554 (12)	C13—H13B	0.9900
C7—H7	1.0000	O1W—H1W1	0.8501
C8—C9	1.532 (13)	O1W—H1W2	0.8520
C8—H8A	0.9900
C6—N1—C2	122.7 (6)	C11—C9—C8	110.8 (7)
C6—N1—C10	123.8 (6)	C10—C9—C8	108.5 (7)
C2—N1—C10	113.5 (6)	C11—C9—H9	107.4
O2—C2—N1	119.8 (7)	C10—C9—H9	107.4
O2—C2—C3	123.2 (7)	C8—C9—H9	107.4
N1—C2—C3	117.0 (7)	N1—C10—C9	114.9 (6)
C2—C3—C4	121.3 (7)	N1—C10—H10A	108.5
C2—C3—H3	119.4	C9—C10—H10A	108.5
C4—C3—H3	119.4	N1—C10—H10B	108.5
C3—C4—C5	118.6 (8)	C9—C10—H10B	108.5
C3—C4—H4	120.7	H10A—C10—H10B	107.5
C5—C4—H4	120.7	N12—C11—C9	112.8 (7)
C6—C5—C4	120.1 (8)	N12—C11—H11A	109.0
C6—C5—H5	120.0	C9—C11—H11A	109.0
C4—C5—H5	120.0	N12—C11—H11B	109.0
C5—C6—N1	120.2 (7)	C9—C11—H11B	109.0
C5—C6—C7	120.6 (7)	H11A—C11—H11B	107.8
N1—C6—C7	119.2 (7)	C11—N12—C13	112.6 (7)
C6—C7—C13	111.4 (7)	C11—N12—H12A	109.1
C6—C7—C8	109.8 (7)	C13—N12—H12A	109.1
C13—C7—C8	110.6 (6)	C11—N12—H12B	109.1
C6—C7—H7	108.3	C13—N12—H12B	109.1
C13—C7—H7	108.3	H12A—N12—H12B	107.8
C8—C7—H7	108.3	N12—C13—C7	111.3 (6)
C9—C8—C7	105.9 (6)	N12—C13—H13A	109.4
C9—C8—H8A	110.6	C7—C13—H13A	109.4
C7—C8—H8A	110.6	N12—C13—H13B	109.4
C9—C8—H8B	110.6	C7—C13—H13B	109.4
C7—C8—H8B	110.6	H13A—C13—H13B	108.0
H8A—C8—H8B	108.7	H1W1—O1W—H1W2	105.1
C11—C9—C10	115.1 (7)
C6—N1—C2—O2	175.7 (7)	C5—C6—C7—C8	−152.3 (7)
C10—N1—C2—O2	−3.7 (11)	N1—C6—C7—C8	27.6 (9)
C6—N1—C2—C3	−5.2 (12)	C6—C7—C8—C9	−61.6 (8)
C10—N1—C2—C3	175.5 (8)	C13—C7—C8—C9	61.8 (8)
O2—C2—C3—C4	−177.0 (8)	C7—C8—C9—C11	−60.4 (8)
N1—C2—C3—C4	3.9 (13)	C7—C8—C9—C10	66.9 (8)
C2—C3—C4—C5	−0.7 (13)	C6—N1—C10—C9	3.0 (11)
C3—C4—C5—C6	−1.6 (12)	C2—N1—C10—C9	−177.6 (7)
C4—C5—C6—N1	0.5 (12)	C11—C9—C10—N1	86.5 (9)
C4—C5—C6—C7	−179.6 (7)	C8—C9—C10—N1	−38.3 (10)
C2—N1—C6—C5	3.1 (11)	C10—C9—C11—N12	−67.1 (9)
C10—N1—C6—C5	−177.7 (8)	C8—C9—C11—N12	56.5 (9)
C2—N1—C6—C7	−176.9 (7)	C9—C11—N12—C13	−50.8 (9)
C10—N1—C6—C7	2.4 (11)	C11—N12—C13—C7	51.4 (8)
C5—C6—C7—C13	84.8 (9)	C6—C7—C13—N12	64.2 (8)
N1—C6—C7—C13	−95.3 (8)	C8—C7—C13—N12	−58.3 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···I1^i	0.99	2.95	3.833 (9)	149
N12—H12B···O1W	0.99	1.85	2.832 (9)	170
N12—H12A···O2^ii	0.99	1.79	2.730 (9)	158
O1W—H1W1···I1^iii	0.85	2.66	3.428 (7)	152
O1W—H1W2···I1	0.85	2.62	3.424 (7)	157

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

6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium nitrate monohydrate (7)

Crystal data

C11H15N2O^+·NO3^−·H2O	F(000) = 288
Mr = 271.27	Dx = 1.457 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.6216 (2) Å	Cell parameters from 19871 reflections
b = 10.4582 (2) Å	θ = 3.7–53.0°
c = 8.4325 (3) Å	µ = 0.12 mm^−1
β = 113.071 (4)°	T = 100 K
V = 618.38 (3) Å^3	Prism, colourless
Z = 2	0.35 × 0.15 × 0.1 mm

Data collection

Agilent Xcalibur Eos diffractometer	3617 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3590 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 16.1544 pixels mm^-1	θmax = 30.1°, θmin = 3.2°
ω scan	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −14→14
Tmin = 0.872, Tmax = 1.000	l = −11→11
19662 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.0644P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max = 0.002
S = 1.09	Δρmax = 0.30 e Å^−3
3617 reflections	Δρmin = −0.19 e Å^−3
240 parameters	Absolute structure: Flack x determined using 1685 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.05 (13)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
N1	0.95931 (14)	0.40399 (10)	0.32980 (13)	0.01352 (18)
C2	1.06476 (17)	0.37541 (12)	0.23143 (17)	0.0159 (2)
O2	1.17702 (13)	0.28201 (9)	0.27516 (14)	0.01958 (19)
C3	1.03688 (18)	0.45697 (13)	0.08786 (17)	0.0194 (2)
H3	1.093 (4)	0.435 (3)	0.008 (3)	0.034 (6)*
C4	0.91851 (19)	0.56031 (13)	0.05414 (17)	0.0192 (2)
H4	0.900 (3)	0.617 (2)	−0.040 (3)	0.031 (6)*
C5	0.81903 (17)	0.58719 (12)	0.16071 (16)	0.0168 (2)
H5	0.739 (3)	0.660 (3)	0.138 (3)	0.031 (6)*
C6	0.84018 (16)	0.50844 (11)	0.29697 (15)	0.0134 (2)
C7	0.73122 (17)	0.53157 (11)	0.41036 (16)	0.0141 (2)
H7	0.708 (3)	0.624 (2)	0.415 (3)	0.020 (5)*
C8	0.83523 (18)	0.47726 (12)	0.59132 (16)	0.0173 (2)
H8A	0.959 (3)	0.517 (2)	0.649 (3)	0.026 (5)*
H8B	0.752 (3)	0.493 (2)	0.654 (3)	0.027 (5)*
C9	0.85826 (19)	0.33464 (12)	0.56937 (17)	0.0172 (2)
H9	0.917 (3)	0.292 (2)	0.683 (3)	0.029 (5)*
C10	0.99042 (18)	0.31428 (12)	0.47442 (16)	0.0169 (2)
H10A	1.118 (3)	0.326 (2)	0.554 (3)	0.017 (4)*
H10B	0.975 (3)	0.230 (2)	0.423 (3)	0.023 (5)*
C11	0.6640 (2)	0.26950 (12)	0.48419 (18)	0.0195 (2)
H11A	0.675 (3)	0.180 (3)	0.462 (3)	0.032 (6)*
H11B	0.591 (3)	0.279 (2)	0.552 (3)	0.018 (4)*
N12	0.54257 (16)	0.33058 (11)	0.31620 (16)	0.0176 (2)
H12A	0.594 (4)	0.303 (3)	0.245 (4)	0.039 (6)*
H12B	0.423 (4)	0.300 (3)	0.284 (3)	0.033 (6)*
C13	0.53195 (17)	0.47259 (12)	0.32892 (17)	0.0165 (2)
H13A	0.461 (3)	0.4927 (19)	0.396 (2)	0.012 (4)*
H13B	0.462 (3)	0.502 (2)	0.217 (3)	0.024 (5)*
O1W	0.70253 (16)	0.19451 (11)	0.12150 (15)	0.0237 (2)
O1A	0.60976 (19)	−0.08245 (13)	0.07588 (16)	0.0323 (3)
N1A	0.55406 (18)	−0.10009 (13)	0.19473 (16)	0.0224 (2)
O2A	0.5814 (2)	−0.01850 (14)	0.30746 (19)	0.0394 (3)
O3A	0.4752 (2)	−0.20366 (12)	0.20401 (16)	0.0343 (3)
H1W1	0.672 (3)	0.111 (2)	0.127 (3)	0.017 (4)*
H1W2	0.657 (4)	0.220 (3)	0.015 (4)	0.048 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0124 (4)	0.0130 (4)	0.0162 (4)	−0.0005 (3)	0.0067 (3)	0.0005 (3)
C2	0.0126 (4)	0.0170 (5)	0.0202 (5)	−0.0030 (4)	0.0085 (4)	−0.0030 (4)
O2	0.0146 (4)	0.0173 (4)	0.0299 (5)	0.0003 (3)	0.0121 (3)	−0.0011 (4)
C3	0.0188 (5)	0.0232 (6)	0.0192 (5)	−0.0031 (5)	0.0107 (4)	−0.0015 (5)
C4	0.0202 (5)	0.0219 (6)	0.0162 (5)	−0.0023 (4)	0.0081 (4)	0.0016 (4)
C5	0.0166 (5)	0.0163 (5)	0.0170 (5)	0.0007 (4)	0.0059 (4)	0.0020 (4)
C6	0.0121 (4)	0.0130 (5)	0.0152 (5)	−0.0010 (4)	0.0054 (4)	−0.0011 (4)
C7	0.0139 (5)	0.0133 (5)	0.0158 (5)	−0.0003 (4)	0.0065 (4)	−0.0020 (4)
C8	0.0202 (5)	0.0169 (5)	0.0147 (5)	−0.0004 (4)	0.0068 (4)	−0.0014 (4)
C9	0.0206 (5)	0.0158 (5)	0.0169 (5)	0.0012 (4)	0.0093 (4)	0.0022 (4)
C10	0.0163 (5)	0.0158 (5)	0.0197 (6)	0.0033 (4)	0.0084 (4)	0.0047 (4)
C11	0.0238 (6)	0.0155 (5)	0.0258 (6)	−0.0032 (4)	0.0168 (5)	−0.0006 (4)
N12	0.0161 (4)	0.0183 (5)	0.0226 (5)	−0.0049 (4)	0.0120 (4)	−0.0066 (4)
C13	0.0136 (4)	0.0171 (5)	0.0198 (5)	−0.0006 (4)	0.0078 (4)	−0.0029 (4)
O1W	0.0266 (5)	0.0230 (5)	0.0233 (5)	−0.0024 (4)	0.0118 (4)	−0.0038 (4)
O1A	0.0402 (6)	0.0381 (6)	0.0270 (5)	0.0001 (5)	0.0222 (5)	0.0038 (5)
N1A	0.0254 (5)	0.0220 (5)	0.0218 (5)	0.0052 (4)	0.0115 (4)	0.0031 (4)
O2A	0.0592 (9)	0.0320 (6)	0.0369 (6)	−0.0096 (6)	0.0296 (6)	−0.0108 (5)
O3A	0.0575 (8)	0.0256 (6)	0.0272 (5)	−0.0063 (5)	0.0247 (6)	0.0005 (4)

Geometric parameters (Å, º)

N1—C6	1.3773 (14)	C9—C10	1.5275 (17)
N1—C2	1.3950 (15)	C9—C11	1.5292 (18)
N1—C10	1.4823 (16)	C9—H9	0.99 (2)
C2—O2	1.2550 (16)	C10—H10A	0.95 (2)
C2—C3	1.4271 (18)	C10—H10B	0.97 (2)
C3—C4	1.3644 (19)	C11—N12	1.4979 (19)
C3—H3	0.96 (3)	C11—H11A	0.97 (3)
C4—C5	1.4127 (17)	C11—H11B	0.95 (2)
C4—H4	0.96 (3)	N12—C13	1.4935 (16)
C5—C6	1.3709 (16)	N12—H12A	0.88 (3)
C5—H5	0.95 (3)	N12—H12B	0.90 (3)
C6—C7	1.5115 (16)	C13—H13A	0.948 (19)
C7—C8	1.5269 (17)	C13—H13B	0.93 (2)
C7—C13	1.5301 (16)	O1W—H1W1	0.91 (2)
C7—H7	0.99 (2)	O1W—H1W2	0.86 (3)
C8—C9	1.5216 (18)	O1A—N1A	1.2459 (16)
C8—H8A	0.97 (2)	N1A—O2A	1.2328 (18)
C8—H8B	0.98 (2)	N1A—O3A	1.2559 (18)
C6—N1—C2	122.58 (10)	C10—C9—C11	114.06 (11)
C6—N1—C10	123.21 (10)	C8—C9—H9	110.7 (15)
C2—N1—C10	114.20 (10)	C10—C9—H9	107.6 (14)
O2—C2—N1	118.51 (11)	C11—C9—H9	104.0 (14)
O2—C2—C3	124.90 (11)	N1—C10—C9	114.67 (10)
N1—C2—C3	116.58 (11)	N1—C10—H10A	106.9 (13)
C4—C3—C2	121.11 (12)	C9—C10—H10A	108.2 (13)
C4—C3—H3	119.2 (15)	N1—C10—H10B	104.5 (13)
C2—C3—H3	119.5 (16)	C9—C10—H10B	112.1 (13)
C3—C4—C5	120.06 (12)	H10A—C10—H10B	110.3 (18)
C3—C4—H4	122.5 (15)	N12—C11—C9	112.33 (10)
C5—C4—H4	117.4 (15)	N12—C11—H11A	107.3 (14)
C6—C5—C4	119.83 (11)	C9—C11—H11A	112.5 (15)
C6—C5—H5	120.3 (15)	N12—C11—H11B	103.6 (12)
C4—C5—H5	119.8 (15)	C9—C11—H11B	110.8 (13)
C5—C6—N1	119.78 (11)	H11A—C11—H11B	109.9 (19)
C5—C6—C7	121.38 (11)	C13—N12—C11	112.76 (10)
N1—C6—C7	118.82 (10)	C13—N12—H12A	115.4 (19)
C6—C7—C8	111.96 (10)	C11—N12—H12A	102.9 (18)
C6—C7—C13	110.26 (10)	C13—N12—H12B	107.5 (18)
C8—C7—C13	109.50 (10)	C11—N12—H12B	108.1 (17)
C6—C7—H7	109.5 (13)	H12A—N12—H12B	110 (3)
C8—C7—H7	111.0 (13)	N12—C13—C7	111.15 (10)
C13—C7—H7	104.4 (13)	N12—C13—H13A	108.8 (12)
C9—C8—C7	106.41 (10)	C7—C13—H13A	110.1 (12)
C9—C8—H8A	110.5 (14)	N12—C13—H13B	106.1 (15)
C7—C8—H8A	111.3 (14)	C7—C13—H13B	113.4 (14)
C9—C8—H8B	111.2 (15)	H13A—C13—H13B	107.1 (18)
C7—C8—H8B	106.2 (14)	H1W1—O1W—H1W2	110 (2)
H8A—C8—H8B	111 (2)	O2A—N1A—O1A	120.66 (14)
C8—C9—C10	109.36 (11)	O2A—N1A—O3A	119.30 (13)
C8—C9—C11	110.93 (11)	O1A—N1A—O3A	120.00 (14)
C6—N1—C2—O2	176.56 (11)	C5—C6—C7—C13	83.95 (14)
C10—N1—C2—O2	−2.04 (15)	N1—C6—C7—C13	−94.45 (12)
C6—N1—C2—C3	−2.86 (16)	C6—C7—C8—C9	−59.05 (13)
C10—N1—C2—C3	178.55 (11)	C13—C7—C8—C9	63.57 (13)
O2—C2—C3—C4	−176.83 (13)	C7—C8—C9—C10	65.52 (13)
N1—C2—C3—C4	2.54 (18)	C7—C8—C9—C11	−61.13 (13)
C2—C3—C4—C5	−0.85 (19)	C6—N1—C10—C9	8.56 (16)
C3—C4—C5—C6	−0.68 (19)	C2—N1—C10—C9	−172.86 (10)
C4—C5—C6—N1	0.41 (17)	C8—C9—C10—N1	−40.93 (15)
C4—C5—C6—C7	−177.97 (11)	C11—C9—C10—N1	83.92 (14)
C2—N1—C6—C5	1.44 (16)	C8—C9—C11—N12	54.91 (14)
C10—N1—C6—C5	179.91 (11)	C10—C9—C11—N12	−69.11 (14)
C2—N1—C6—C7	179.87 (10)	C9—C11—N12—C13	−49.50 (14)
C10—N1—C6—C7	−1.67 (16)	C11—N12—C13—C7	52.04 (13)
C5—C6—C7—C8	−153.87 (11)	C6—C7—C13—N12	63.66 (13)
N1—C6—C7—C8	27.73 (14)	C8—C7—C13—N12	−59.96 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2A	0.97 (3)	2.40 (3)	3.3097 (19)	156 (2)
C11—H11B···O3A^i	0.95 (2)	2.31 (2)	3.2101 (18)	158.9 (17)
N12—H12A···O1W	0.88 (3)	1.93 (3)	2.7885 (16)	163 (3)
N12—H12B···O2^ii	0.90 (3)	1.86 (3)	2.7174 (15)	159 (3)
C13—H13B···O1A^iii	0.93 (2)	2.47 (2)	3.2031 (18)	135.0 (19)
O1W—H1W1···O1A	0.91 (2)	2.08 (2)	2.9706 (18)	164.3 (19)
O1W—H1W1···O2A	0.91 (2)	2.33 (2)	3.0673 (19)	137.5 (18)
O1W—H1W2···O3A^iii	0.86 (3)	1.90 (3)	2.7549 (18)	168 (3)

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

Hydrogen bis(6-oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium) tribromide (8)

Crystal data

C22H31N4O2^3+·3Br^−	F(000) = 624
Mr = 623.24	Dx = 1.714 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 10.78898 (14) Å	Cell parameters from 4853 reflections
b = 7.84934 (11) Å	θ = 3.1–75.1°
c = 14.37986 (17) Å	µ = 6.41 mm^−1
β = 97.4435 (12)°	T = 130 K
V = 1207.52 (3) Å^3	Prism, pale red
Z = 2	0.35 × 0.15 × 0.15 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	3843 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	3835 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 5.2679 pixels mm^-1	θmax = 75.4°, θmin = 3.1°
ω scan	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −9→9
Tmin = 0.391, Tmax = 1.000	l = −16→17
5286 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 0.5197P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.064	(Δ/σ)max = 0.001
S = 1.13	Δρmax = 0.45 e Å^−3
3843 reflections	Δρmin = −0.50 e Å^−3
280 parameters	Absolute structure: Flack x determined using 1235 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.007 (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
N1A	0.3748 (3)	0.8219 (4)	0.1300 (2)	0.0145 (6)
C2A	0.4453 (3)	0.6835 (5)	0.1630 (3)	0.0160 (7)
O2A	0.4911 (2)	0.6859 (4)	0.2496 (2)	0.0214 (6)
H2	0.5193	0.5486	0.2855	0.026*
C3A	0.4626 (3)	0.5503 (6)	0.1001 (3)	0.0204 (8)
H3A	0.5129	0.4548	0.1208	0.024*
C4A	0.4069 (4)	0.5588 (5)	0.0094 (3)	0.0210 (8)
H4A	0.4175	0.4681	−0.0326	0.025*
C5A	0.3344 (4)	0.6999 (6)	−0.0222 (3)	0.0200 (8)
H5A	0.2959	0.7047	−0.0854	0.024*
C6A	0.3189 (3)	0.8317 (5)	0.0382 (3)	0.0156 (7)
C7A	0.2367 (4)	0.9825 (6)	0.0085 (3)	0.0199 (8)
H7A	0.2436	1.0078	−0.0588	0.024*
C8A	0.2760 (4)	1.1407 (6)	0.0662 (3)	0.0217 (8)
H8A	0.2197	1.2371	0.0463	0.026*
H8B	0.3625	1.1735	0.0582	0.026*
C9A	0.2675 (4)	1.0944 (6)	0.1687 (3)	0.0201 (8)
H9A	0.2899	1.1985	0.2073	0.024*
C10A	0.3634 (4)	0.9585 (5)	0.2007 (3)	0.0189 (7)
H10A	0.4460	1.0138	0.2165	0.023*
H10B	0.3410	0.9053	0.2586	0.023*
C11A	0.1339 (4)	1.0467 (6)	0.1811 (3)	0.0215 (8)
H11A	0.1312	1.0112	0.2469	0.026*
H11B	0.0798	1.1482	0.1689	0.026*
N12A	0.0836 (3)	0.9063 (5)	0.1174 (2)	0.0203 (7)
H12A	0.0009	0.8927	0.1219	0.024*
H12B	0.1232	0.8076	0.1365	0.024*
C13A	0.0994 (4)	0.9380 (6)	0.0170 (3)	0.0223 (8)
H13A	0.0446	1.0331	−0.0078	0.027*
H13B	0.0746	0.8351	−0.0206	0.027*
N1B	0.6912 (3)	0.2097 (5)	0.3658 (2)	0.0146 (6)
C2B	0.6614 (3)	0.3610 (5)	0.3215 (2)	0.0171 (7)
O2B	0.5475 (3)	0.4113 (5)	0.3214 (2)	0.0264 (7)
C3B	0.7525 (4)	0.4503 (5)	0.2800 (3)	0.0195 (8)
H3B	0.7331	0.5563	0.2497	0.023*
C4B	0.8699 (4)	0.3821 (6)	0.2839 (3)	0.0219 (8)
H4B	0.9326	0.4413	0.2562	0.026*
C5B	0.8979 (3)	0.2266 (6)	0.3282 (3)	0.0209 (8)
H5B	0.9794	0.1799	0.3303	0.025*
C6B	0.8084 (3)	0.1406 (5)	0.3689 (2)	0.0155 (7)
C7B	0.8334 (4)	−0.0308 (6)	0.4145 (3)	0.0223 (8)
H7B	0.8946	−0.0924	0.3800	0.027*
C8B	0.7137 (5)	−0.1368 (6)	0.4071 (3)	0.0278 (9)
H8C	0.6780	−0.1518	0.3407	0.033*
H8D	0.7309	−0.2505	0.4356	0.033*
C9B	0.6236 (4)	−0.0377 (6)	0.4601 (3)	0.0248 (9)
H9B	0.5453	−0.1066	0.4576	0.030*
C10B	0.5890 (3)	0.1302 (6)	0.4114 (3)	0.0202 (8)
H10C	0.5162	0.1113	0.3631	0.024*
H10D	0.5630	0.2111	0.4580	0.024*
C11B	0.6761 (4)	−0.0171 (6)	0.5633 (3)	0.0257 (9)
H11C	0.6177	0.0526	0.5952	0.031*
H11D	0.6829	−0.1305	0.5937	0.031*
N12B	0.8015 (3)	0.0661 (5)	0.5747 (2)	0.0200 (7)
H12C	0.7920	0.1778	0.5586	0.024*
H12D	0.8343	0.0614	0.6362	0.024*
C13B	0.8911 (4)	−0.0136 (6)	0.5173 (3)	0.0248 (9)
H13C	0.9152	−0.1277	0.5429	0.030*
H13D	0.9676	0.0570	0.5210	0.030*
Br1	0.77209 (4)	0.47581 (5)	0.56257 (3)	0.02476 (12)
Br2	0.15819 (3)	0.52783 (5)	0.19735 (2)	0.01681 (10)
Br3	0.80557 (4)	0.85617 (5)	0.16266 (3)	0.02158 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0151 (12)	0.0121 (16)	0.0168 (14)	−0.0026 (12)	0.0038 (11)	−0.0011 (12)
C2A	0.0133 (14)	0.0153 (19)	0.0201 (17)	0.0010 (15)	0.0047 (13)	0.0016 (15)
O2A	0.0207 (12)	0.0219 (16)	0.0207 (13)	0.0049 (12)	−0.0008 (10)	0.0001 (11)
C3A	0.0170 (15)	0.017 (2)	0.0278 (19)	0.0038 (15)	0.0046 (14)	0.0015 (16)
C4A	0.0230 (17)	0.018 (2)	0.0242 (19)	−0.0004 (16)	0.0102 (14)	−0.0037 (16)
C5A	0.0220 (17)	0.020 (2)	0.0190 (18)	−0.0029 (16)	0.0061 (14)	−0.0024 (16)
C6A	0.0190 (15)	0.0153 (19)	0.0131 (16)	−0.0021 (15)	0.0043 (12)	0.0028 (14)
C7A	0.0293 (19)	0.0157 (19)	0.0152 (16)	0.0031 (16)	0.0043 (14)	0.0033 (15)
C8A	0.0290 (19)	0.0131 (19)	0.0236 (19)	0.0032 (16)	0.0057 (15)	0.0070 (16)
C9A	0.0274 (19)	0.0148 (18)	0.0186 (17)	0.0027 (16)	0.0044 (14)	−0.0027 (15)
C10A	0.0238 (17)	0.0159 (19)	0.0165 (17)	−0.0003 (16)	0.0005 (13)	−0.0043 (15)
C11A	0.0259 (18)	0.021 (2)	0.0176 (17)	0.0072 (18)	0.0044 (14)	−0.0016 (16)
N12A	0.0189 (14)	0.0191 (16)	0.0234 (16)	0.0038 (13)	0.0045 (12)	0.0052 (14)
C13A	0.0234 (18)	0.023 (2)	0.0191 (19)	0.0046 (17)	−0.0013 (14)	0.0015 (16)
N1B	0.0149 (13)	0.0150 (15)	0.0142 (14)	0.0018 (13)	0.0034 (11)	0.0027 (12)
C2B	0.0180 (15)	0.0194 (19)	0.0141 (16)	0.0034 (16)	0.0035 (12)	0.0000 (15)
O2B	0.0198 (12)	0.0317 (17)	0.0284 (15)	0.0112 (13)	0.0064 (11)	0.0119 (13)
C3B	0.0248 (18)	0.017 (2)	0.0167 (17)	−0.0021 (16)	0.0033 (14)	0.0020 (15)
C4B	0.0196 (16)	0.025 (2)	0.0219 (18)	−0.0070 (17)	0.0070 (14)	−0.0016 (17)
C5B	0.0164 (16)	0.029 (2)	0.0185 (17)	0.0022 (16)	0.0049 (13)	−0.0032 (16)
C6B	0.0157 (16)	0.0169 (19)	0.0140 (15)	0.0035 (15)	0.0023 (12)	−0.0045 (15)
C7B	0.0310 (19)	0.021 (2)	0.0155 (17)	0.0099 (18)	0.0039 (15)	−0.0011 (16)
C8B	0.046 (2)	0.0142 (19)	0.0219 (19)	−0.0024 (19)	0.0006 (17)	−0.0006 (17)
C9B	0.0287 (19)	0.022 (2)	0.024 (2)	−0.0116 (18)	0.0020 (15)	0.0047 (17)
C10B	0.0151 (16)	0.025 (2)	0.0212 (17)	−0.0032 (16)	0.0060 (13)	0.0056 (17)
C11B	0.0292 (19)	0.027 (2)	0.0212 (19)	−0.0043 (18)	0.0060 (15)	0.0069 (18)
N12B	0.0291 (16)	0.0174 (19)	0.0132 (14)	−0.0003 (14)	0.0024 (12)	−0.0004 (12)
C13B	0.0263 (19)	0.029 (2)	0.0183 (18)	0.0098 (18)	−0.0002 (15)	0.0022 (17)
Br1	0.0393 (2)	0.0170 (2)	0.01784 (19)	−0.00075 (17)	0.00327 (16)	0.00058 (15)
Br2	0.01994 (17)	0.01452 (19)	0.01677 (17)	−0.00014 (14)	0.00542 (12)	0.00124 (14)
Br3	0.02320 (19)	0.0224 (2)	0.01936 (19)	−0.00164 (16)	0.00354 (13)	0.00037 (16)

Geometric parameters (Å, º)

N1A—C2A	1.375 (5)	N1B—C2B	1.366 (5)
N1A—C6A	1.382 (5)	N1B—C6B	1.372 (5)
N1A—C10A	1.493 (5)	N1B—C10B	1.491 (5)
C2A—O2A	1.279 (5)	C2B—O2B	1.290 (5)
C2A—C3A	1.411 (6)	C2B—C3B	1.402 (6)
O2A—H2	1.2169	O2B—H2	1.2165
C3A—C4A	1.365 (6)	C3B—C4B	1.370 (6)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.397 (6)	C4B—C5B	1.392 (6)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.375 (6)	C5B—C6B	1.370 (6)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—C7A	1.507 (6)	C6B—C7B	1.506 (6)
C7A—C8A	1.523 (6)	C7B—C8B	1.529 (6)
C7A—C13A	1.542 (5)	C7B—C13B	1.534 (5)
C7A—H7A	1.0000	C7B—H7B	1.0000
C8A—C9A	1.532 (5)	C8B—C9B	1.523 (7)
C8A—H8A	0.9900	C8B—H8C	0.9900
C8A—H8B	0.9900	C8B—H8D	0.9900
C9A—C10A	1.516 (6)	C9B—C10B	1.516 (6)
C9A—C11A	1.522 (6)	C9B—C11B	1.527 (6)
C9A—H9A	1.0000	C9B—H9B	1.0000
C10A—H10A	0.9900	C10B—H10C	0.9900
C10A—H10B	0.9900	C10B—H10D	0.9900
C11A—N12A	1.490 (6)	C11B—N12B	1.492 (5)
C11A—H11A	0.9900	C11B—H11C	0.9900
C11A—H11B	0.9900	C11B—H11D	0.9900
N12A—C13A	1.495 (5)	N12B—C13B	1.488 (5)
N12A—H12A	0.9100	N12B—H12C	0.9100
N12A—H12B	0.9100	N12B—H12D	0.9100
C13A—H13A	0.9900	C13B—H13C	0.9900
C13A—H13B	0.9900	C13B—H13D	0.9900
C2A—N1A—C6A	121.8 (3)	C2B—N1B—C6B	121.3 (3)
C2A—N1A—C10A	115.1 (3)	C2B—N1B—C10B	115.2 (3)
C6A—N1A—C10A	123.2 (3)	C6B—N1B—C10B	123.5 (3)
O2A—C2A—N1A	116.8 (4)	O2B—C2B—N1B	115.7 (4)
O2A—C2A—C3A	124.7 (4)	O2B—C2B—C3B	124.5 (4)
N1A—C2A—C3A	118.6 (3)	N1B—C2B—C3B	119.8 (3)
C2A—O2A—H2	116.4	C2B—O2B—H2	117.2
C4A—C3A—C2A	119.9 (4)	C4B—C3B—C2B	118.9 (4)
C4A—C3A—H3A	120.1	C4B—C3B—H3B	120.6
C2A—C3A—H3A	120.1	C2B—C3B—H3B	120.6
C3A—C4A—C5A	120.5 (4)	C3B—C4B—C5B	120.4 (4)
C3A—C4A—H4A	119.7	C3B—C4B—H4B	119.8
C5A—C4A—H4A	119.7	C5B—C4B—H4B	119.8
C6A—C5A—C4A	120.0 (4)	C6B—C5B—C4B	120.3 (4)
C6A—C5A—H5A	120.0	C6B—C5B—H5B	119.9
C4A—C5A—H5A	120.0	C4B—C5B—H5B	119.9
C5A—C6A—N1A	119.3 (4)	C5B—C6B—N1B	119.3 (4)
C5A—C6A—C7A	121.9 (3)	C5B—C6B—C7B	122.0 (3)
N1A—C6A—C7A	118.8 (3)	N1B—C6B—C7B	118.7 (3)
C6A—C7A—C8A	112.0 (3)	C6B—C7B—C8B	110.7 (3)
C6A—C7A—C13A	109.6 (3)	C6B—C7B—C13B	111.6 (4)
C8A—C7A—C13A	110.1 (3)	C8B—C7B—C13B	110.4 (3)
C6A—C7A—H7A	108.3	C6B—C7B—H7B	108.0
C8A—C7A—H7A	108.3	C8B—C7B—H7B	108.0
C13A—C7A—H7A	108.3	C13B—C7B—H7B	108.0
C7A—C8A—C9A	106.5 (3)	C9B—C8B—C7B	106.0 (4)
C7A—C8A—H8A	110.4	C9B—C8B—H8C	110.5
C9A—C8A—H8A	110.4	C7B—C8B—H8C	110.5
C7A—C8A—H8B	110.4	C9B—C8B—H8D	110.5
C9A—C8A—H8B	110.4	C7B—C8B—H8D	110.5
H8A—C8A—H8B	108.6	H8C—C8B—H8D	108.7
C10A—C9A—C11A	114.3 (4)	C10B—C9B—C8B	110.3 (3)
C10A—C9A—C8A	109.6 (3)	C10B—C9B—C11B	113.3 (4)
C11A—C9A—C8A	110.3 (3)	C8B—C9B—C11B	111.1 (4)
C10A—C9A—H9A	107.5	C10B—C9B—H9B	107.3
C11A—C9A—H9A	107.5	C8B—C9B—H9B	107.3
C8A—C9A—H9A	107.5	C11B—C9B—H9B	107.3
N1A—C10A—C9A	114.3 (3)	N1B—C10B—C9B	114.5 (3)
N1A—C10A—H10A	108.7	N1B—C10B—H10C	108.6
C9A—C10A—H10A	108.7	C9B—C10B—H10C	108.6
N1A—C10A—H10B	108.7	N1B—C10B—H10D	108.6
C9A—C10A—H10B	108.7	C9B—C10B—H10D	108.6
H10A—C10A—H10B	107.6	H10C—C10B—H10D	107.6
N12A—C11A—C9A	112.6 (3)	N12B—C11B—C9B	111.7 (3)
N12A—C11A—H11A	109.1	N12B—C11B—H11C	109.3
C9A—C11A—H11A	109.1	C9B—C11B—H11C	109.3
N12A—C11A—H11B	109.1	N12B—C11B—H11D	109.3
C9A—C11A—H11B	109.1	C9B—C11B—H11D	109.3
H11A—C11A—H11B	107.8	H11C—C11B—H11D	107.9
C11A—N12A—C13A	113.1 (3)	C13B—N12B—C11B	113.6 (3)
C11A—N12A—H12A	109.0	C13B—N12B—H12C	108.8
C13A—N12A—H12A	109.0	C11B—N12B—H12C	108.8
C11A—N12A—H12B	109.0	C13B—N12B—H12D	108.8
C13A—N12A—H12B	109.0	C11B—N12B—H12D	108.8
H12A—N12A—H12B	107.8	H12C—N12B—H12D	107.7
N12A—C13A—C7A	110.2 (3)	N12B—C13B—C7B	111.1 (3)
N12A—C13A—H13A	109.6	N12B—C13B—H13C	109.4
C7A—C13A—H13A	109.6	C7B—C13B—H13C	109.4
N12A—C13A—H13B	109.6	N12B—C13B—H13D	109.4
C7A—C13A—H13B	109.6	C7B—C13B—H13D	109.4
H13A—C13A—H13B	108.1	H13C—C13B—H13D	108.0
C6A—N1A—C2A—O2A	−178.8 (3)	C6B—N1B—C2B—O2B	178.5 (3)
C10A—N1A—C2A—O2A	1.0 (5)	C10B—N1B—C2B—O2B	−2.9 (5)
C6A—N1A—C2A—C3A	1.4 (5)	C6B—N1B—C2B—C3B	−1.5 (5)
C10A—N1A—C2A—C3A	−178.8 (3)	C10B—N1B—C2B—C3B	177.1 (4)
O2A—C2A—C3A—C4A	178.4 (4)	O2B—C2B—C3B—C4B	−179.2 (4)
N1A—C2A—C3A—C4A	−1.8 (6)	N1B—C2B—C3B—C4B	0.8 (6)
C2A—C3A—C4A—C5A	1.1 (6)	C2B—C3B—C4B—C5B	0.1 (6)
C3A—C4A—C5A—C6A	0.1 (6)	C3B—C4B—C5B—C6B	−0.4 (6)
C4A—C5A—C6A—N1A	−0.5 (6)	C4B—C5B—C6B—N1B	−0.3 (6)
C4A—C5A—C6A—C7A	−177.1 (4)	C4B—C5B—C6B—C7B	177.8 (4)
C2A—N1A—C6A—C5A	−0.2 (5)	C2B—N1B—C6B—C5B	1.2 (5)
C10A—N1A—C6A—C5A	179.9 (3)	C10B—N1B—C6B—C5B	−177.3 (4)
C2A—N1A—C6A—C7A	176.4 (3)	C2B—N1B—C6B—C7B	−176.9 (3)
C10A—N1A—C6A—C7A	−3.4 (5)	C10B—N1B—C6B—C7B	4.6 (5)
C5A—C6A—C7A—C8A	−154.7 (4)	C5B—C6B—C7B—C8B	−150.0 (4)
N1A—C6A—C7A—C8A	28.7 (5)	N1B—C6B—C7B—C8B	28.0 (5)
C5A—C6A—C7A—C13A	82.8 (4)	C5B—C6B—C7B—C13B	86.5 (4)
N1A—C6A—C7A—C13A	−93.8 (4)	N1B—C6B—C7B—C13B	−95.4 (4)
C6A—C7A—C8A—C9A	−59.0 (4)	C6B—C7B—C8B—C9B	−61.8 (4)
C13A—C7A—C8A—C9A	63.2 (4)	C13B—C7B—C8B—C9B	62.4 (4)
C7A—C8A—C9A—C10A	65.7 (4)	C7B—C8B—C9B—C10B	65.0 (4)
C7A—C8A—C9A—C11A	−61.0 (4)	C7B—C8B—C9B—C11B	−61.5 (5)
C2A—N1A—C10A—C9A	−169.6 (3)	C2B—N1B—C10B—C9B	179.9 (3)
C6A—N1A—C10A—C9A	10.3 (5)	C6B—N1B—C10B—C9B	−1.5 (5)
C11A—C9A—C10A—N1A	82.9 (4)	C8B—C9B—C10B—N1B	−34.1 (5)
C8A—C9A—C10A—N1A	−41.5 (5)	C11B—C9B—C10B—N1B	91.2 (4)
C10A—C9A—C11A—N12A	−68.3 (4)	C10B—C9B—C11B—N12B	−68.7 (5)
C8A—C9A—C11A—N12A	55.7 (5)	C8B—C9B—C11B—N12B	56.1 (5)
C9A—C11A—N12A—C13A	−51.1 (4)	C9B—C11B—N12B—C13B	−50.0 (5)
C11A—N12A—C13A—C7A	52.0 (4)	C11B—N12B—C13B—C7B	51.0 (5)
C6A—C7A—C13A—N12A	64.3 (4)	C6B—C7B—C13B—N12B	65.6 (5)
C8A—C7A—C13A—N12A	−59.3 (4)	C8B—C7B—C13B—N12B	−58.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2B—H2···O2A	1.22	1.22	2.433 (4)	180
N12A—H12A···Br3^i	0.91	2.28	3.176 (3)	169
N12A—H12B···Br2	0.91	2.38	3.249 (4)	161
N12B—H12C···Br1	0.91	2.35	3.234 (4)	164
N12B—H12D···Br2^ii	0.91	2.40	3.264 (3)	159

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

Hydrogen bis(6-Oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium) triiodide (9)

Crystal data

C22H31N4O2^+·3I^−	Dx = 1.753 Mg m^−3
Mr = 764.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2627 reflections
a = 7.9767 (3) Å	θ = 3.3–25.6°
b = 14.1131 (6) Å	µ = 3.26 mm^−1
c = 25.725 (1) Å	T = 295 K
V = 2896.0 (2) Å^3	Prism, colourless
Z = 4	0.3 × 0.1 × 0.1 mm
F(000) = 1464

Data collection

Agilent Xcalibur Eos diffractometer	4691 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3988 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.1544 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ω scan	h = −9→6
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −16→11
Tmin = 0.022, Tmax = 0.043	l = −30→16
7561 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.048	w = 1/[σ^2(Fo^2) + (0.0866P)^2 + 3.3053P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.140	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 1.76 e Å^−3
4691 reflections	Δρmin = −0.99 e Å^−3
280 parameters	Absolute structure: Flack x determined using 1314 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.00 (2)

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
N1A	0.3344 (14)	0.4689 (8)	0.5077 (4)	0.048 (3)
C2A	0.4929 (19)	0.4793 (11)	0.5288 (6)	0.058 (4)
O2A	0.5461 (15)	0.4104 (8)	0.5567 (4)	0.074 (3)
H2	0.6707	0.4096	0.5833	0.088*
C3A	0.5730 (17)	0.5623 (11)	0.5196 (7)	0.059 (4)
H3A	0.6790	0.5709	0.5339	0.071*
C4A	0.511 (2)	0.6290 (13)	0.4926 (7)	0.078 (5)
H4A	0.5720	0.6845	0.4878	0.094*
C5A	0.346 (2)	0.6191 (12)	0.4691 (7)	0.076 (5)
H5A	0.3004	0.6664	0.4484	0.091*
C6A	0.2626 (17)	0.5373 (10)	0.4790 (6)	0.050 (3)
C7A	0.0874 (17)	0.5204 (11)	0.4561 (6)	0.059 (4)
H7A	0.0293	0.5815	0.4540	0.071*
C8A	−0.0137 (19)	0.4547 (12)	0.4921 (7)	0.067 (4)
H8A	−0.0241	0.4824	0.5265	0.080*
H8B	−0.1251	0.4441	0.4782	0.080*
C9A	0.0833 (19)	0.3626 (12)	0.4947 (6)	0.066 (4)
H9A	0.0183	0.3189	0.5163	0.079*
C10A	0.252 (2)	0.3785 (13)	0.5221 (6)	0.070 (4)
H10A	0.2338	0.3776	0.5594	0.084*
H10B	0.3264	0.3264	0.5136	0.084*
C11A	0.097 (2)	0.3182 (11)	0.4408 (6)	0.064 (4)
H11A	0.1638	0.2609	0.4429	0.077*
H11B	−0.0143	0.3006	0.4288	0.077*
N12A	0.1728 (15)	0.3830 (10)	0.4034 (5)	0.063 (3)
H12A	0.1657	0.3573	0.3719	0.076*
H12B	0.2811	0.3890	0.4110	0.076*
C13A	0.0971 (19)	0.4784 (11)	0.4016 (6)	0.062 (4)
H13A	−0.0147	0.4744	0.3869	0.074*
H13B	0.1640	0.5193	0.3795	0.074*
N1B	0.8990 (14)	0.4397 (7)	0.6892 (4)	0.044 (2)
C2B	0.7742 (16)	0.4472 (9)	0.6527 (5)	0.044 (3)
O2B	0.7959 (11)	0.4088 (7)	0.6097 (4)	0.053 (2)
C3B	0.6321 (17)	0.4999 (10)	0.6676 (6)	0.054 (3)
H3B	0.5430	0.5066	0.6446	0.065*
C4B	0.6243 (17)	0.5402 (11)	0.7146 (7)	0.068 (4)
H4B	0.5316	0.5769	0.7233	0.082*
C5B	0.7498 (18)	0.5287 (10)	0.7502 (6)	0.060 (4)
H5B	0.7386	0.5537	0.7835	0.072*
C6B	0.8929 (18)	0.4798 (9)	0.7368 (5)	0.047 (3)
C7B	1.0365 (19)	0.4666 (10)	0.7748 (6)	0.055 (3)
H7B	1.0473	0.5243	0.7957	0.066*
C8B	1.2016 (18)	0.4506 (13)	0.7455 (7)	0.067 (5)
H8C	1.2276	0.5049	0.7238	0.080*
H8D	1.2931	0.4409	0.7697	0.080*
C9B	1.1757 (17)	0.3633 (11)	0.7124 (6)	0.062 (4)
H9B	1.2827	0.3490	0.6955	0.074*
C10B	1.0473 (15)	0.3840 (11)	0.6694 (5)	0.053 (3)
H10C	1.1016	0.4194	0.6418	0.064*
H10D	1.0082	0.3246	0.6549	0.064*
C11B	1.131 (2)	0.2782 (12)	0.7473 (6)	0.069 (4)
H11C	1.1026	0.2249	0.7251	0.083*
H11D	1.2295	0.2607	0.7671	0.083*
N12B	0.9945 (18)	0.2938 (8)	0.7829 (5)	0.064 (3)
H12D	0.9930	0.2465	0.8057	0.077*
H12C	0.8989	0.2915	0.7651	0.077*
C13B	1.000 (3)	0.3833 (12)	0.8115 (5)	0.071 (5)
H13C	1.0866	0.3799	0.8379	0.085*
H13D	0.8935	0.3935	0.8288	0.085*
I1	0.60502 (11)	0.36832 (7)	0.39825 (4)	0.0609 (3)
I2	0.62829 (13)	0.23083 (7)	0.71423 (4)	0.0612 (3)
I3	0.9668 (2)	0.14717 (8)	0.88852 (5)	0.0889 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.055 (6)	0.054 (6)	0.033 (5)	−0.008 (5)	−0.008 (5)	−0.005 (5)
C2A	0.066 (9)	0.060 (9)	0.049 (8)	0.010 (8)	−0.001 (7)	−0.019 (7)
O2A	0.085 (7)	0.067 (7)	0.069 (7)	0.013 (6)	−0.034 (6)	−0.002 (6)
C3A	0.042 (7)	0.061 (9)	0.075 (10)	−0.004 (6)	−0.014 (7)	−0.006 (8)
C4A	0.080 (10)	0.064 (10)	0.092 (13)	−0.023 (10)	−0.013 (10)	−0.004 (10)
C5A	0.078 (10)	0.057 (9)	0.094 (12)	0.001 (9)	−0.026 (10)	0.008 (9)
C6A	0.049 (7)	0.043 (7)	0.060 (8)	0.004 (6)	−0.007 (7)	−0.009 (7)
C7A	0.044 (7)	0.067 (9)	0.067 (9)	0.012 (7)	−0.019 (7)	−0.008 (8)
C8A	0.048 (8)	0.085 (11)	0.067 (10)	0.005 (8)	0.004 (7)	−0.028 (9)
C9A	0.061 (9)	0.071 (10)	0.067 (9)	−0.026 (8)	−0.009 (7)	0.018 (8)
C10A	0.071 (9)	0.078 (11)	0.062 (9)	−0.007 (9)	−0.026 (8)	0.027 (9)
C11A	0.061 (9)	0.059 (8)	0.073 (10)	−0.009 (8)	−0.015 (9)	0.011 (8)
N12A	0.055 (6)	0.088 (9)	0.046 (7)	−0.016 (6)	−0.010 (5)	−0.011 (7)
C13A	0.054 (7)	0.067 (9)	0.065 (9)	−0.007 (7)	−0.013 (8)	0.010 (8)
N1B	0.044 (5)	0.042 (5)	0.047 (6)	0.003 (5)	0.010 (5)	0.003 (5)
C2B	0.044 (7)	0.045 (7)	0.044 (7)	−0.012 (6)	−0.009 (6)	0.017 (6)
O2B	0.057 (5)	0.064 (6)	0.039 (5)	0.006 (4)	−0.005 (4)	−0.011 (5)
C3B	0.041 (7)	0.063 (8)	0.058 (8)	0.003 (7)	−0.005 (7)	−0.001 (7)
C4B	0.032 (6)	0.065 (9)	0.108 (13)	0.011 (7)	0.013 (9)	−0.004 (10)
C5B	0.057 (9)	0.051 (9)	0.072 (10)	−0.007 (7)	0.016 (8)	−0.015 (8)
C6B	0.055 (7)	0.043 (7)	0.043 (7)	−0.003 (7)	0.004 (7)	−0.006 (6)
C7B	0.067 (8)	0.052 (8)	0.046 (8)	0.004 (7)	−0.006 (7)	−0.010 (7)
C8B	0.045 (7)	0.085 (12)	0.071 (11)	−0.011 (8)	−0.024 (7)	0.024 (9)
C9B	0.049 (7)	0.070 (9)	0.066 (9)	0.003 (7)	0.000 (7)	−0.009 (9)
C10B	0.042 (6)	0.072 (9)	0.045 (7)	0.017 (7)	0.006 (6)	0.001 (7)
C11B	0.085 (11)	0.069 (10)	0.053 (8)	0.012 (10)	−0.012 (9)	0.016 (7)
N12B	0.077 (8)	0.061 (7)	0.055 (8)	−0.003 (6)	−0.016 (7)	0.018 (6)
C13B	0.105 (12)	0.081 (11)	0.027 (6)	−0.025 (10)	−0.013 (8)	0.003 (7)
I1	0.0501 (4)	0.0767 (6)	0.0559 (5)	−0.0021 (5)	−0.0039 (4)	−0.0046 (5)
I2	0.0637 (5)	0.0665 (6)	0.0535 (5)	−0.0156 (5)	0.0083 (5)	−0.0045 (5)
I3	0.1333 (11)	0.0658 (6)	0.0677 (7)	0.0224 (7)	0.0156 (7)	0.0109 (6)

Geometric parameters (Å, º)

N1A—C6A	1.345 (18)	N1B—C6B	1.350 (16)
N1A—C2A	1.384 (19)	N1B—C2B	1.372 (16)
N1A—C10A	1.48 (2)	N1B—C10B	1.509 (16)
C2A—O2A	1.281 (18)	C2B—O2B	1.245 (16)
C2A—C3A	1.35 (2)	C2B—C3B	1.41 (2)
O2A—H2	1.2074	O2B—H2	1.2076
C3A—C4A	1.27 (2)	C3B—C4B	1.34 (2)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.46 (3)	C4B—C5B	1.37 (2)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.36 (2)	C5B—C6B	1.38 (2)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.535 (19)	C6B—C7B	1.52 (2)
C7A—C13A	1.52 (2)	C7B—C8B	1.53 (2)
C7A—C8A	1.54 (2)	C7B—C13B	1.54 (2)
C7A—H7A	0.9800	C7B—H7B	0.9800
C8A—C9A	1.51 (2)	C8B—C9B	1.51 (2)
C8A—H8A	0.9700	C8B—H8C	0.9700
C8A—H8B	0.9700	C8B—H8D	0.9700
C9A—C11A	1.53 (2)	C9B—C10B	1.535 (19)
C9A—C10A	1.534 (19)	C9B—C11B	1.54 (2)
C9A—H9A	0.9800	C9B—H9B	0.9800
C10A—H10A	0.9700	C10B—H10C	0.9700
C10A—H10B	0.9700	C10B—H10D	0.9700
C11A—N12A	1.460 (19)	C11B—N12B	1.44 (2)
C11A—H11A	0.9700	C11B—H11C	0.9700
C11A—H11B	0.9700	C11B—H11D	0.9700
N12A—C13A	1.48 (2)	N12B—C13B	1.46 (2)
N12A—H12A	0.8900	N12B—H12D	0.8900
N12A—H12B	0.8900	N12B—H12C	0.8900
C13A—H13A	0.9700	C13B—H13C	0.9700
C13A—H13B	0.9700	C13B—H13D	0.9700
C6A—N1A—C2A	121.9 (12)	C6B—N1B—C2B	124.2 (12)
C6A—N1A—C10A	124.4 (11)	C6B—N1B—C10B	123.6 (11)
C2A—N1A—C10A	113.6 (11)	C2B—N1B—C10B	112.3 (10)
O2A—C2A—C3A	126.7 (15)	O2B—C2B—N1B	118.2 (12)
O2A—C2A—N1A	116.1 (14)	O2B—C2B—C3B	125.7 (12)
C3A—C2A—N1A	117.1 (14)	N1B—C2B—C3B	116.1 (13)
C2A—O2A—H2	126.7	C2B—O2B—H2	112.4
C4A—C3A—C2A	123.6 (15)	C4B—C3B—C2B	120.4 (13)
C4A—C3A—H3A	118.2	C4B—C3B—H3B	119.8
C2A—C3A—H3A	118.2	C2B—C3B—H3B	119.8
C3A—C4A—C5A	120.5 (16)	C3B—C4B—C5B	121.4 (13)
C3A—C4A—H4A	119.8	C3B—C4B—H4B	119.3
C5A—C4A—H4A	119.8	C5B—C4B—H4B	119.3
C6A—C5A—C4A	116.7 (15)	C4B—C5B—C6B	119.9 (14)
C6A—C5A—H5A	121.7	C4B—C5B—H5B	120.0
C4A—C5A—H5A	121.7	C6B—C5B—H5B	120.0
N1A—C6A—C5A	120.3 (13)	N1B—C6B—C5B	117.9 (13)
N1A—C6A—C7A	119.1 (12)	N1B—C6B—C7B	120.4 (12)
C5A—C6A—C7A	120.5 (14)	C5B—C6B—C7B	121.7 (12)
C13A—C7A—C6A	111.5 (12)	C6B—C7B—C8B	110.4 (11)
C13A—C7A—C8A	110.3 (13)	C6B—C7B—C13B	110.3 (13)
C6A—C7A—C8A	109.9 (12)	C8B—C7B—C13B	110.6 (14)
C13A—C7A—H7A	108.4	C6B—C7B—H7B	108.5
C6A—C7A—H7A	108.4	C8B—C7B—H7B	108.5
C8A—C7A—H7A	108.4	C13B—C7B—H7B	108.5
C9A—C8A—C7A	106.0 (12)	C9B—C8B—C7B	106.2 (12)
C9A—C8A—H8A	110.5	C9B—C8B—H8C	110.5
C7A—C8A—H8A	110.5	C7B—C8B—H8C	110.5
C9A—C8A—H8B	110.5	C9B—C8B—H8D	110.5
C7A—C8A—H8B	110.5	C7B—C8B—H8D	110.5
H8A—C8A—H8B	108.7	H8C—C8B—H8D	108.7
C8A—C9A—C11A	110.5 (13)	C8B—C9B—C10B	110.0 (12)
C8A—C9A—C10A	110.0 (14)	C8B—C9B—C11B	109.9 (13)
C11A—C9A—C10A	114.6 (15)	C10B—C9B—C11B	114.4 (13)
C8A—C9A—H9A	107.1	C8B—C9B—H9B	107.4
C11A—C9A—H9A	107.1	C10B—C9B—H9B	107.4
C10A—C9A—H9A	107.1	C11B—C9B—H9B	107.4
N1A—C10A—C9A	113.6 (11)	N1B—C10B—C9B	112.3 (11)
N1A—C10A—H10A	108.8	N1B—C10B—H10C	109.2
C9A—C10A—H10A	108.8	C9B—C10B—H10C	109.2
N1A—C10A—H10B	108.8	N1B—C10B—H10D	109.2
C9A—C10A—H10B	108.8	C9B—C10B—H10D	109.2
H10A—C10A—H10B	107.7	H10C—C10B—H10D	107.9
N12A—C11A—C9A	111.7 (12)	N12B—C11B—C9B	115.2 (13)
N12A—C11A—H11A	109.3	N12B—C11B—H11C	108.5
C9A—C11A—H11A	109.3	C9B—C11B—H11C	108.5
N12A—C11A—H11B	109.3	N12B—C11B—H11D	108.5
C9A—C11A—H11B	109.3	C9B—C11B—H11D	108.5
H11A—C11A—H11B	107.9	H11C—C11B—H11D	107.5
C11A—N12A—C13A	114.9 (12)	C11B—N12B—C13B	115.5 (14)
C11A—N12A—H12A	108.5	C11B—N12B—H12D	108.4
C13A—N12A—H12A	108.5	C13B—N12B—H12D	108.4
C11A—N12A—H12B	108.5	C11B—N12B—H12C	108.4
C13A—N12A—H12B	108.5	C13B—N12B—H12C	108.4
H12A—N12A—H12B	107.5	H12D—N12B—H12C	107.5
N12A—C13A—C7A	110.3 (12)	N12B—C13B—C7B	111.0 (11)
N12A—C13A—H13A	109.6	N12B—C13B—H13C	109.4
C7A—C13A—H13A	109.6	C7B—C13B—H13C	109.4
N12A—C13A—H13B	109.6	N12B—C13B—H13D	109.4
C7A—C13A—H13B	109.6	C7B—C13B—H13D	109.4
H13A—C13A—H13B	108.1	H13C—C13B—H13D	108.0
C6A—N1A—C2A—O2A	178.1 (13)	C6B—N1B—C2B—O2B	178.4 (12)
C10A—N1A—C2A—O2A	0.8 (18)	C10B—N1B—C2B—O2B	0.3 (16)
C6A—N1A—C2A—C3A	0.6 (19)	C6B—N1B—C2B—C3B	−0.6 (17)
C10A—N1A—C2A—C3A	−176.7 (14)	C10B—N1B—C2B—C3B	−178.8 (12)
O2A—C2A—C3A—C4A	−178.1 (18)	O2B—C2B—C3B—C4B	−178.2 (14)
N1A—C2A—C3A—C4A	−1 (2)	N1B—C2B—C3B—C4B	1 (2)
C2A—C3A—C4A—C5A	0 (3)	C2B—C3B—C4B—C5B	−3 (2)
C3A—C4A—C5A—C6A	2 (3)	C3B—C4B—C5B—C6B	4 (2)
C2A—N1A—C6A—C5A	1 (2)	C2B—N1B—C6B—C5B	2.3 (18)
C10A—N1A—C6A—C5A	178.0 (15)	C10B—N1B—C6B—C5B	−179.8 (12)
C2A—N1A—C6A—C7A	179.2 (12)	C2B—N1B—C6B—C7B	179.2 (12)
C10A—N1A—C6A—C7A	−4 (2)	C10B—N1B—C6B—C7B	−2.8 (19)
C4A—C5A—C6A—N1A	−2 (2)	C4B—C5B—C6B—N1B	−4 (2)
C4A—C5A—C6A—C7A	179.7 (14)	C4B—C5B—C6B—C7B	179.0 (13)
N1A—C6A—C7A—C13A	−91.9 (16)	N1B—C6B—C7B—C8B	27.8 (18)
C5A—C6A—C7A—C13A	86.3 (18)	C5B—C6B—C7B—C8B	−155.4 (14)
N1A—C6A—C7A—C8A	30.7 (18)	N1B—C6B—C7B—C13B	−94.8 (16)
C5A—C6A—C7A—C8A	−151.2 (15)	C5B—C6B—C7B—C13B	82.1 (16)
C13A—C7A—C8A—C9A	62.6 (15)	C6B—C7B—C8B—C9B	−59.0 (15)
C6A—C7A—C8A—C9A	−60.7 (15)	C13B—C7B—C8B—C9B	63.3 (15)
C7A—C8A—C9A—C11A	−61.3 (15)	C7B—C8B—C9B—C10B	67.8 (15)
C7A—C8A—C9A—C10A	66.2 (16)	C7B—C8B—C9B—C11B	−59.0 (16)
C6A—N1A—C10A—C9A	8 (2)	C6B—N1B—C10B—C9B	10.1 (18)
C2A—N1A—C10A—C9A	−174.6 (13)	C2B—N1B—C10B—C9B	−171.8 (11)
C8A—C9A—C10A—N1A	−40.0 (19)	C8B—C9B—C10B—N1B	−42.9 (17)
C11A—C9A—C10A—N1A	85.2 (18)	C11B—C9B—C10B—N1B	81.3 (16)
C8A—C9A—C11A—N12A	56.2 (17)	C8B—C9B—C11B—N12B	51.9 (18)
C10A—C9A—C11A—N12A	−68.7 (17)	C10B—C9B—C11B—N12B	−72.3 (17)
C9A—C11A—N12A—C13A	−50.8 (17)	C9B—C11B—N12B—C13B	−45.7 (18)
C11A—N12A—C13A—C7A	51.5 (16)	C11B—N12B—C13B—C7B	47.4 (19)
C6A—C7A—C13A—N12A	64.9 (16)	C6B—C7B—C13B—N12B	65.3 (18)
C8A—C7A—C13A—N12A	−57.5 (15)	C8B—C7B—C13B—N12B	−57.1 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2···O2B	1.21	1.21	2.415 (13)	180
N12A—H12A···I2^i	0.89	2.56	3.444 (12)	174
N12A—H12B···I1	0.89	2.62	3.456 (12)	157
N12B—H12D···I3	0.89	2.56	3.423 (12)	164
N12B—H12C···I2	0.89	2.67	3.528 (13)	163

Symmetry code: (i) x−1/2, −y+1/2, −z+1.

Hydrogen bis(6-oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium) triiodide diiodide (10)

Crystal data

C22H31N4O2·I3^−·2I^−	Dx = 2.240 Mg m^−3
Mr = 1018.01	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4485 reflections
a = 7.8269 (2) Å	θ = 3.2–27.7°
b = 19.3211 (6) Å	µ = 5.18 mm^−1
c = 19.9592 (5) Å	T = 100 K
V = 3018.32 (14) Å^3	Plate, pale-purple
Z = 4	0.13 × 0.1 × 0.03 mm
F(000) = 1888

Data collection

Agilent Xcalibur Eos diffractometer	5927 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5420 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 16.1544 pixels mm^-1	θmax = 28.2°, θmin = 3.2°
ω scan	h = −10→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −22→24
Tmin = 0.769, Tmax = 1.000	l = −25→7
8661 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0152P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.053	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 1.02 e Å^−3
5927 reflections	Δρmin = −0.71 e Å^−3
298 parameters	Absolute structure: Flack x determined using 1967 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.04 (2)

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
N1A	−0.1054 (7)	0.5162 (3)	0.5064 (3)	0.0120 (13)
C2A	0.0279 (9)	0.4772 (4)	0.4834 (4)	0.0168 (17)
O2A	0.0156 (6)	0.4559 (3)	0.4217 (3)	0.0192 (12)
H2A	0.1216	0.4132	0.4052	0.023*
C3A	0.1662 (9)	0.4628 (4)	0.5254 (4)	0.0203 (18)
H3A	0.2598	0.4380	0.5096	0.024*
C4A	0.1612 (10)	0.4859 (4)	0.5901 (4)	0.0258 (19)
H4A	0.2533	0.4773	0.6183	0.031*
C5A	0.0195 (10)	0.5222 (4)	0.6146 (4)	0.0239 (18)
H5A	0.0156	0.5363	0.6591	0.029*
C6A	−0.1137 (9)	0.5368 (4)	0.5721 (4)	0.0154 (16)
C7A	−0.2664 (9)	0.5773 (4)	0.5958 (4)	0.0202 (18)
H7A	−0.2922	0.5632	0.6419	0.024*
C8A	−0.4224 (8)	0.5627 (4)	0.5527 (4)	0.0206 (18)
H8A1	−0.4538	0.5142	0.5557	0.025*
H8A2	−0.5185	0.5904	0.5676	0.025*
C9A	−0.3752 (9)	0.5811 (4)	0.4810 (4)	0.0172 (16)
H9A	−0.4771	0.5732	0.4535	0.021*
C10A	−0.2388 (9)	0.5328 (4)	0.4558 (4)	0.0189 (17)
H10A	−0.2922	0.4901	0.4412	0.023*
H10B	−0.1842	0.5536	0.4170	0.023*
C11A	−0.3348 (9)	0.6582 (4)	0.4772 (4)	0.0201 (17)
H11A	−0.2968	0.6693	0.4322	0.024*
H11B	−0.4383	0.6843	0.4858	0.024*
N12A	−0.2005 (7)	0.6799 (3)	0.5260 (3)	0.0189 (13)
H12A	−0.0910	0.6622	0.5111	0.023*
H12B	−0.1935	0.7301	0.5261	0.023*
C13A	−0.2314 (9)	0.6558 (4)	0.5955 (4)	0.0186 (17)
H13A	−0.3287	0.6802	0.6142	0.022*
H13B	−0.1323	0.6659	0.6230	0.022*
N1B	0.4782 (7)	0.3382 (3)	0.3417 (3)	0.0148 (13)
C2B	0.3642 (9)	0.3895 (4)	0.3596 (4)	0.0179 (17)
O2B	0.2277 (6)	0.3704 (3)	0.3888 (3)	0.0225 (13)
C3B	0.4088 (9)	0.4594 (4)	0.3434 (4)	0.0207 (18)
H3B	0.3356	0.4956	0.3544	0.025*
C4B	0.5593 (10)	0.4722 (4)	0.3120 (4)	0.026 (2)
H4B	0.5900	0.5177	0.3026	0.031*
C5B	0.6679 (10)	0.4190 (4)	0.2938 (4)	0.0227 (19)
H5B	0.7695	0.4289	0.2716	0.027*
C6B	0.6266 (8)	0.3523 (4)	0.3083 (3)	0.0171 (15)
C7B	0.7433 (9)	0.2931 (4)	0.2887 (4)	0.0230 (18)
H7B	0.8031	0.3059	0.2474	0.028*
C8B	0.6421 (9)	0.2271 (4)	0.2755 (4)	0.0253 (19)
H8B1	0.5610	0.2343	0.2394	0.030*
H8B2	0.7183	0.1897	0.2631	0.030*
C9B	0.5494 (9)	0.2101 (4)	0.3400 (4)	0.0182 (17)
H9B	0.4845	0.1675	0.3321	0.022*
C10B	0.4206 (8)	0.2664 (4)	0.3581 (4)	0.0185 (18)
H10C	0.3146	0.2572	0.3345	0.022*
H10D	0.3970	0.2637	0.4057	0.022*
C11B	0.6782 (9)	0.1946 (4)	0.3956 (4)	0.0241 (19)
H11C	0.6171	0.1855	0.4370	0.029*
H11D	0.7421	0.1533	0.3841	0.029*
N12B	0.7995 (8)	0.2529 (3)	0.4064 (3)	0.0228 (15)
H12C	0.7392	0.2903	0.4285	0.027*
H12D	0.8895	0.2375	0.4362	0.027*
C13B	0.8787 (9)	0.2802 (4)	0.3440 (4)	0.0229 (18)
H13C	0.9627	0.2474	0.3277	0.027*
H13D	0.9373	0.3232	0.3539	0.027*
I1C	0.76399 (7)	0.81504 (3)	0.32477 (3)	0.03429 (15)
I2C	0.86628 (6)	0.67458 (3)	0.28284 (2)	0.02120 (12)
I3C	1.01319 (7)	0.54495 (3)	0.23841 (3)	0.02838 (14)
I1D	0.62384 (6)	0.35152 (3)	0.53099 (2)	0.01853 (11)
I1E	0.68521 (5)	0.84860 (3)	0.55592 (3)	0.01826 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.008 (3)	0.014 (3)	0.014 (3)	0.001 (3)	−0.002 (2)	0.002 (3)
C2A	0.015 (4)	0.014 (4)	0.021 (4)	0.002 (3)	0.000 (3)	0.003 (3)
O2A	0.014 (3)	0.026 (3)	0.018 (3)	0.004 (2)	0.000 (2)	−0.008 (3)
C3A	0.012 (4)	0.018 (4)	0.030 (4)	0.006 (3)	−0.003 (4)	0.000 (4)
C4A	0.024 (4)	0.022 (4)	0.032 (5)	0.000 (4)	−0.011 (4)	0.004 (4)
C5A	0.030 (5)	0.021 (4)	0.020 (4)	−0.002 (4)	−0.006 (4)	−0.005 (4)
C6A	0.019 (4)	0.014 (4)	0.014 (4)	0.000 (3)	−0.001 (3)	−0.001 (3)
C7A	0.026 (4)	0.018 (4)	0.017 (4)	0.005 (3)	0.003 (3)	0.003 (4)
C8A	0.011 (4)	0.019 (4)	0.032 (4)	0.000 (3)	0.008 (3)	−0.006 (4)
C9A	0.010 (3)	0.022 (4)	0.020 (4)	0.005 (3)	−0.007 (3)	−0.001 (4)
C10A	0.019 (4)	0.018 (4)	0.019 (4)	0.002 (3)	−0.004 (3)	−0.001 (4)
C11A	0.017 (4)	0.024 (4)	0.019 (4)	0.008 (3)	−0.005 (3)	−0.003 (4)
N12A	0.018 (3)	0.011 (3)	0.028 (3)	0.000 (3)	0.005 (3)	−0.001 (3)
C13A	0.017 (4)	0.021 (4)	0.017 (4)	0.003 (3)	0.004 (3)	0.000 (4)
N1B	0.012 (3)	0.021 (4)	0.011 (3)	0.001 (3)	0.001 (3)	0.001 (3)
C2B	0.017 (4)	0.018 (4)	0.018 (4)	0.006 (3)	−0.005 (3)	−0.006 (3)
O2B	0.013 (3)	0.022 (3)	0.033 (3)	0.005 (2)	0.005 (2)	−0.009 (3)
C3B	0.023 (4)	0.014 (4)	0.025 (4)	0.004 (3)	−0.011 (4)	0.002 (4)
C4B	0.034 (5)	0.023 (4)	0.021 (4)	−0.007 (4)	−0.006 (4)	0.005 (4)
C5B	0.019 (4)	0.030 (5)	0.019 (4)	−0.010 (3)	0.002 (3)	0.001 (4)
C6B	0.012 (3)	0.028 (4)	0.011 (3)	−0.002 (4)	−0.001 (3)	−0.002 (4)
C7B	0.015 (4)	0.037 (5)	0.018 (4)	0.000 (4)	0.004 (3)	−0.003 (4)
C8B	0.015 (4)	0.035 (5)	0.026 (4)	0.003 (4)	−0.006 (4)	−0.014 (4)
C9B	0.016 (4)	0.013 (4)	0.025 (4)	0.001 (3)	−0.002 (3)	−0.002 (4)
C10B	0.012 (4)	0.017 (4)	0.026 (4)	−0.003 (3)	0.003 (3)	−0.005 (4)
C11B	0.023 (4)	0.019 (4)	0.030 (5)	0.007 (3)	0.000 (4)	0.001 (4)
N12B	0.022 (3)	0.030 (4)	0.017 (3)	0.007 (3)	−0.001 (3)	−0.002 (3)
C13B	0.010 (3)	0.034 (5)	0.025 (4)	−0.001 (4)	0.001 (4)	−0.012 (4)
I1C	0.0257 (3)	0.0402 (3)	0.0370 (3)	0.0035 (3)	−0.0080 (3)	−0.0154 (3)
I2C	0.0168 (2)	0.0319 (3)	0.0148 (2)	−0.0031 (2)	0.0007 (2)	0.0028 (2)
I3C	0.0304 (3)	0.0285 (3)	0.0263 (3)	−0.0063 (2)	0.0077 (3)	0.0003 (3)
I1D	0.0198 (2)	0.0172 (2)	0.0185 (2)	−0.0010 (2)	0.0037 (2)	−0.0008 (2)
I1E	0.0124 (2)	0.0167 (2)	0.0257 (3)	0.00000 (19)	0.0010 (2)	−0.0016 (2)

Geometric parameters (Å, º)

N1A—C2A	1.367 (9)	N1B—C2B	1.380 (9)
N1A—C6A	1.372 (9)	N1B—C10B	1.496 (9)
N1A—C10A	1.488 (9)	C2B—O2B	1.272 (9)
C2A—O2A	1.302 (9)	C2B—C3B	1.432 (10)
C2A—C3A	1.396 (10)	O2B—H2A	1.2163
O2A—H2A	1.2163	C3B—C4B	1.357 (11)
C3A—C4A	1.368 (11)	C3B—H3B	0.9300
C3A—H3A	0.9300	C4B—C5B	1.383 (11)
C4A—C5A	1.400 (11)	C4B—H4B	0.9300
C4A—H4A	0.9300	C5B—C6B	1.359 (10)
C5A—C6A	1.373 (10)	C5B—H5B	0.9300
C5A—H5A	0.9300	C6B—C7B	1.515 (10)
C6A—C7A	1.505 (10)	C7B—C8B	1.524 (10)
C7A—C8A	1.521 (10)	C7B—C13B	1.550 (10)
C7A—C13A	1.543 (10)	C7B—H7B	0.9800
C7A—H7A	0.9800	C8B—C9B	1.514 (11)
C8A—C9A	1.520 (11)	C8B—H8B1	0.9700
C8A—H8A1	0.9700	C8B—H8B2	0.9700
C8A—H8A2	0.9700	C9B—C10B	1.526 (9)
C9A—C10A	1.505 (10)	C9B—C11B	1.529 (10)
C9A—C11A	1.525 (10)	C9B—H9B	0.9800
C9A—H9A	0.9800	C10B—H10C	0.9700
C10A—H10A	0.9700	C10B—H10D	0.9700
C10A—H10B	0.9700	C11B—N12B	1.488 (9)
C11A—N12A	1.494 (9)	C11B—H11C	0.9700
C11A—H11A	0.9700	C11B—H11D	0.9700
C11A—H11B	0.9700	N12B—C13B	1.488 (9)
N12A—C13A	1.481 (9)	N12B—H12C	0.9700
N12A—H12A	0.9700	N12B—H12D	0.9700
N12A—H12B	0.9700	C13B—H13C	0.9700
C13A—H13A	0.9700	C13B—H13D	0.9700
C13A—H13B	0.9700	I1C—I2C	2.9506 (8)
N1B—C6B	1.367 (8)	I2C—I3C	2.8950 (8)
C2A—N1A—C6A	121.1 (6)	C6B—N1B—C10B	123.2 (6)
C2A—N1A—C10A	115.3 (6)	C2B—N1B—C10B	114.5 (5)
C6A—N1A—C10A	123.6 (6)	O2B—C2B—N1B	117.0 (6)
O2A—C2A—N1A	115.8 (6)	O2B—C2B—C3B	125.6 (7)
O2A—C2A—C3A	124.2 (7)	N1B—C2B—C3B	117.4 (7)
N1A—C2A—C3A	120.0 (7)	C2B—O2B—H2A	120.0
C2A—O2A—H2A	114.8	C4B—C3B—C2B	119.2 (7)
C4A—C3A—C2A	118.7 (7)	C4B—C3B—H3B	120.4
C4A—C3A—H3A	120.7	C2B—C3B—H3B	120.4
C2A—C3A—H3A	120.7	C3B—C4B—C5B	121.2 (8)
C3A—C4A—C5A	121.0 (7)	C3B—C4B—H4B	119.4
C3A—C4A—H4A	119.5	C5B—C4B—H4B	119.4
C5A—C4A—H4A	119.5	C6B—C5B—C4B	120.2 (7)
C6A—C5A—C4A	119.2 (7)	C6B—C5B—H5B	119.9
C6A—C5A—H5A	120.4	C4B—C5B—H5B	119.9
C4A—C5A—H5A	120.4	C5B—C6B—N1B	119.6 (7)
N1A—C6A—C5A	119.7 (7)	C5B—C6B—C7B	121.2 (7)
N1A—C6A—C7A	119.2 (6)	N1B—C6B—C7B	119.2 (7)
C5A—C6A—C7A	121.0 (7)	C6B—C7B—C8B	111.3 (6)
C6A—C7A—C8A	111.3 (6)	C6B—C7B—C13B	110.5 (6)
C6A—C7A—C13A	111.7 (6)	C8B—C7B—C13B	110.1 (7)
C8A—C7A—C13A	108.8 (6)	C6B—C7B—H7B	108.3
C6A—C7A—H7A	108.3	C8B—C7B—H7B	108.3
C8A—C7A—H7A	108.3	C13B—C7B—H7B	108.3
C13A—C7A—H7A	108.3	C9B—C8B—C7B	106.5 (6)
C9A—C8A—C7A	107.1 (6)	C9B—C8B—H8B1	110.4
C9A—C8A—H8A1	110.3	C7B—C8B—H8B1	110.4
C7A—C8A—H8A1	110.3	C9B—C8B—H8B2	110.4
C9A—C8A—H8A2	110.3	C7B—C8B—H8B2	110.4
C7A—C8A—H8A2	110.3	H8B1—C8B—H8B2	108.6
H8A1—C8A—H8A2	108.6	C8B—C9B—C10B	111.2 (6)
C10A—C9A—C8A	110.0 (6)	C8B—C9B—C11B	110.1 (6)
C10A—C9A—C11A	116.2 (6)	C10B—C9B—C11B	113.7 (6)
C8A—C9A—C11A	109.0 (6)	C8B—C9B—H9B	107.1
C10A—C9A—H9A	107.1	C10B—C9B—H9B	107.1
C8A—C9A—H9A	107.1	C11B—C9B—H9B	107.1
C11A—C9A—H9A	107.1	N1B—C10B—C9B	114.2 (6)
N1A—C10A—C9A	113.9 (6)	N1B—C10B—H10C	108.7
N1A—C10A—H10A	108.8	C9B—C10B—H10C	108.7
C9A—C10A—H10A	108.8	N1B—C10B—H10D	108.7
N1A—C10A—H10B	108.8	C9B—C10B—H10D	108.7
C9A—C10A—H10B	108.8	H10C—C10B—H10D	107.6
H10A—C10A—H10B	107.7	N12B—C11B—C9B	112.2 (6)
N12A—C11A—C9A	112.8 (6)	N12B—C11B—H11C	109.2
N12A—C11A—H11A	109.0	C9B—C11B—H11C	109.2
C9A—C11A—H11A	109.0	N12B—C11B—H11D	109.2
N12A—C11A—H11B	109.0	C9B—C11B—H11D	109.2
C9A—C11A—H11B	109.0	H11C—C11B—H11D	107.9
H11A—C11A—H11B	107.8	C13B—N12B—C11B	114.4 (6)
C13A—N12A—C11A	114.0 (5)	C13B—N12B—H12C	108.7
C13A—N12A—H12A	108.7	C11B—N12B—H12C	108.7
C11A—N12A—H12A	108.7	C13B—N12B—H12D	108.7
C13A—N12A—H12B	108.7	C11B—N12B—H12D	108.7
C11A—N12A—H12B	108.7	H12C—N12B—H12D	107.6
H12A—N12A—H12B	107.6	N12B—C13B—C7B	111.6 (6)
N12A—C13A—C7A	110.0 (6)	N12B—C13B—H13C	109.3
N12A—C13A—H13A	109.7	C7B—C13B—H13C	109.3
C7A—C13A—H13A	109.7	N12B—C13B—H13D	109.3
N12A—C13A—H13B	109.7	C7B—C13B—H13D	109.3
C7A—C13A—H13B	109.7	H13C—C13B—H13D	108.0
H13A—C13A—H13B	108.2	I3C—I2C—I1C	172.03 (2)
C6B—N1B—C2B	122.2 (6)
C6A—N1A—C2A—O2A	174.6 (6)	C6B—N1B—C2B—O2B	177.9 (6)
C10A—N1A—C2A—O2A	−4.3 (9)	C10B—N1B—C2B—O2B	1.6 (9)
C6A—N1A—C2A—C3A	−5.7 (11)	C6B—N1B—C2B—C3B	−1.7 (10)
C10A—N1A—C2A—C3A	175.3 (6)	C10B—N1B—C2B—C3B	−178.1 (6)
O2A—C2A—C3A—C4A	−177.6 (7)	O2B—C2B—C3B—C4B	−179.9 (7)
N1A—C2A—C3A—C4A	2.8 (11)	N1B—C2B—C3B—C4B	−0.3 (11)
C2A—C3A—C4A—C5A	1.1 (11)	C2B—C3B—C4B—C5B	1.7 (12)
C3A—C4A—C5A—C6A	−2.2 (12)	C3B—C4B—C5B—C6B	−1.1 (12)
C2A—N1A—C6A—C5A	4.5 (10)	C4B—C5B—C6B—N1B	−0.9 (11)
C10A—N1A—C6A—C5A	−176.6 (7)	C4B—C5B—C6B—C7B	179.9 (7)
C2A—N1A—C6A—C7A	−177.6 (6)	C2B—N1B—C6B—C5B	2.3 (10)
C10A—N1A—C6A—C7A	1.3 (10)	C10B—N1B—C6B—C5B	178.4 (7)
C4A—C5A—C6A—N1A	−0.6 (11)	C2B—N1B—C6B—C7B	−178.5 (6)
C4A—C5A—C6A—C7A	−178.4 (7)	C10B—N1B—C6B—C7B	−2.4 (10)
N1A—C6A—C7A—C8A	25.3 (9)	C5B—C6B—C7B—C8B	−150.2 (7)
C5A—C6A—C7A—C8A	−156.8 (7)	N1B—C6B—C7B—C8B	30.6 (9)
N1A—C6A—C7A—C13A	−96.6 (8)	C5B—C6B—C7B—C13B	87.1 (9)
C5A—C6A—C7A—C13A	81.3 (9)	N1B—C6B—C7B—C13B	−92.1 (7)
C6A—C7A—C8A—C9A	−57.9 (8)	C6B—C7B—C8B—C9B	−60.1 (8)
C13A—C7A—C8A—C9A	65.7 (7)	C13B—C7B—C8B—C9B	62.9 (7)
C7A—C8A—C9A—C10A	65.9 (7)	C7B—C8B—C9B—C10B	63.7 (7)
C7A—C8A—C9A—C11A	−62.6 (7)	C7B—C8B—C9B—C11B	−63.4 (8)
C2A—N1A—C10A—C9A	−174.7 (6)	C6B—N1B—C10B—C9B	5.3 (10)
C6A—N1A—C10A—C9A	6.4 (9)	C2B—N1B—C10B—C9B	−178.3 (6)
C8A—C9A—C10A—N1A	−40.0 (8)	C8B—C9B—C10B—N1B	−36.7 (9)
C11A—C9A—C10A—N1A	84.4 (8)	C11B—C9B—C10B—N1B	88.3 (8)
C10A—C9A—C11A—N12A	−70.3 (8)	C8B—C9B—C11B—N12B	56.7 (8)
C8A—C9A—C11A—N12A	54.7 (8)	C10B—C9B—C11B—N12B	−68.9 (8)
C9A—C11A—N12A—C13A	−49.6 (8)	C9B—C11B—N12B—C13B	−48.6 (8)
C11A—N12A—C13A—C7A	51.2 (8)	C11B—N12B—C13B—C7B	47.8 (8)
C6A—C7A—C13A—N12A	63.7 (8)	C6B—C7B—C13B—N12B	67.9 (8)
C8A—C7A—C13A—N12A	−59.6 (8)	C8B—C7B—C13B—N12B	−55.5 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O2B	1.22	1.22	2.433 (7)	180
C9A—H9A···I1E^i	0.98	3.05	3.771 (7)	132
N12A—H12A···I1E^ii	0.97	2.55	3.478 (6)	160
N12A—H12B···I1E^iii	0.97	2.55	3.432 (6)	151
C5B—H5B···I3C	0.93	3.02	3.801 (7)	143
N12B—H12C···I1D	0.97	2.53	3.421 (6)	153
N12B—H12D···I1D^iv	0.97	2.60	3.475 (6)	151
C13B—H13C···I2C^v	0.97	2.94	3.816 (8)	151
C13B—H13D···O2B^vi	0.97	2.55	3.361 (9)	142

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

Hydrogen bis(6-oxo-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium) bis(triodide) iodide (11)

Crystal data

C22H31N4O2·2I3^−·I^−	Dx = 2.530 Mg m^−3
Mr = 1271.81	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 7126 reflections
a = 7.8686 (2) Å	θ = 3.0–73.4°
b = 19.4183 (5) Å	µ = 51.29 mm^−1
c = 21.8550 (6) Å	T = 295 K
V = 3339.33 (15) Å^3	Prism, red
Z = 4	0.1 × 0.05 × 0.05 mm
F(000) = 2312

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	5659 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	4860 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.061
Detector resolution: 10.5357 pixels mm^-1	θmax = 67.5°, θmin = 3.0°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −18→23
Tmin = 0.010, Tmax = 1.000	l = −26→22
17041 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 3.6611P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.135	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.92 e Å^−3
5659 reflections	Δρmin = −0.73 e Å^−3
316 parameters	Absolute structure: Flack x determined using 1649 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.03 (2)

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
N1A	0.0112 (19)	0.6381 (7)	0.3688 (7)	0.036 (3)
C2A	0.123 (3)	0.5913 (11)	0.3919 (9)	0.047 (5)
O2A	0.2532 (19)	0.6169 (7)	0.4201 (7)	0.053 (4)
H2	0.3660	0.5787	0.4387	0.064*
C3A	0.085 (3)	0.5219 (11)	0.3852 (10)	0.053 (5)
H3A	0.1563	0.4892	0.4026	0.064*
C4A	−0.050 (3)	0.5014 (11)	0.3545 (11)	0.062 (6)
H4A	−0.0701	0.4547	0.3487	0.074*
C5A	−0.163 (3)	0.5494 (10)	0.3310 (11)	0.053 (5)
H5A	−0.2610	0.5344	0.3111	0.064*
C6A	−0.133 (3)	0.6180 (10)	0.3365 (8)	0.042 (4)
C7A	−0.249 (3)	0.6731 (10)	0.3116 (9)	0.047 (5)
H7A	−0.3000	0.6550	0.2740	0.057*
C8A	−0.154 (3)	0.7362 (13)	0.2949 (11)	0.062 (6)
H8A1	−0.2313	0.7707	0.2788	0.074*
H8A2	−0.0694	0.7260	0.2641	0.074*
C9A	−0.071 (3)	0.7621 (10)	0.3525 (12)	0.054 (6)
H9A	−0.0093	0.8043	0.3417	0.064*
C10A	0.060 (3)	0.7111 (10)	0.3753 (12)	0.051 (5)
H10A	0.1653	0.7186	0.3533	0.061*
H10B	0.0816	0.7203	0.4183	0.061*
C11A	−0.207 (3)	0.7819 (11)	0.3994 (12)	0.062 (6)
H11A	−0.1521	0.7950	0.4374	0.074*
H11B	−0.2692	0.8216	0.3844	0.074*
N12A	−0.328 (3)	0.7255 (9)	0.4117 (8)	0.055 (5)
H12A	−0.4237	0.7441	0.4343	0.066*
H12B	−0.2726	0.6918	0.4377	0.066*
C13A	−0.394 (3)	0.6896 (10)	0.3558 (10)	0.048 (5)
H13A	−0.4769	0.7187	0.3355	0.058*
H13B	−0.4505	0.6472	0.3678	0.058*
N1B	0.6108 (19)	0.4907 (7)	0.5373 (7)	0.034 (3)
C2B	0.475 (2)	0.5277 (8)	0.5146 (9)	0.037 (4)
O2B	0.4789 (19)	0.5407 (7)	0.4573 (6)	0.049 (3)
C3B	0.342 (3)	0.5470 (10)	0.5544 (10)	0.047 (5)
H3B	0.2467	0.5699	0.5397	0.057*
C4B	0.357 (3)	0.5314 (10)	0.6147 (10)	0.052 (5)
H4B	0.2707	0.5440	0.6414	0.062*
C5B	0.498 (3)	0.4970 (10)	0.6378 (10)	0.048 (5)
H5B	0.5050	0.4869	0.6794	0.057*
C6B	0.629 (3)	0.4777 (8)	0.5982 (9)	0.038 (4)
C7B	0.779 (3)	0.4392 (10)	0.6208 (9)	0.046 (5)
H7B	0.8080	0.4579	0.6611	0.055*
C8B	0.931 (3)	0.4508 (12)	0.5798 (10)	0.053 (5)
H8B1	1.0288	0.4258	0.5950	0.064*
H8B2	0.9589	0.4994	0.5779	0.064*
C9B	0.879 (2)	0.4239 (10)	0.5158 (10)	0.047 (5)
H9B	0.9774	0.4294	0.4888	0.056*
C10B	0.738 (3)	0.4696 (10)	0.4914 (8)	0.041 (4)
H10C	0.7888	0.5106	0.4739	0.050*
H10D	0.6803	0.4453	0.4586	0.050*
C11B	0.838 (3)	0.3479 (10)	0.5189 (11)	0.053 (5)
H11C	0.7950	0.3329	0.4795	0.064*
H11D	0.9413	0.3224	0.5273	0.064*
N12B	0.708 (2)	0.3315 (8)	0.5676 (8)	0.049 (4)
H12C	0.5978	0.3479	0.5540	0.059*
H12D	0.7005	0.2819	0.5720	0.059*
C13B	0.746 (3)	0.3624 (10)	0.6290 (10)	0.051 (5)
H13C	0.8449	0.3403	0.6468	0.061*
H13D	0.6504	0.3554	0.6564	0.061*
I1C	0.4543 (2)	0.20479 (7)	0.64121 (7)	0.0579 (4)
I2C	0.26748 (18)	0.32122 (7)	0.69203 (7)	0.0509 (3)
I3C	0.12708 (19)	0.44341 (7)	0.75007 (7)	0.0552 (4)
I1D	0.5942 (2)	0.37140 (8)	0.21863 (8)	0.0696 (5)
I2D	0.4680 (2)	0.36566 (7)	0.33833 (8)	0.0596 (4)
I3D	0.33615 (18)	0.34907 (7)	0.47501 (7)	0.0516 (3)
I1E	0.8587 (2)	0.65724 (6)	0.54184 (6)	0.0530 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.035 (8)	0.037 (7)	0.036 (7)	0.010 (7)	0.002 (7)	0.007 (6)
C2A	0.042 (12)	0.058 (12)	0.042 (10)	0.019 (10)	0.018 (10)	0.016 (9)
O2A	0.034 (8)	0.059 (8)	0.067 (10)	0.003 (7)	−0.002 (7)	0.016 (7)
C3A	0.058 (14)	0.042 (11)	0.059 (13)	0.007 (10)	−0.003 (12)	0.010 (9)
C4A	0.074 (17)	0.037 (10)	0.075 (16)	0.006 (11)	0.005 (15)	−0.010 (10)
C5A	0.044 (11)	0.044 (10)	0.071 (14)	−0.004 (10)	−0.012 (11)	−0.004 (10)
C6A	0.041 (11)	0.052 (10)	0.035 (9)	0.006 (9)	0.003 (9)	0.006 (8)
C7A	0.053 (12)	0.053 (11)	0.037 (9)	0.006 (10)	−0.005 (10)	0.004 (9)
C8A	0.060 (15)	0.071 (14)	0.055 (13)	0.021 (13)	0.010 (13)	0.021 (11)
C9A	0.033 (10)	0.039 (10)	0.089 (17)	0.003 (8)	0.004 (11)	0.027 (11)
C10A	0.039 (11)	0.035 (9)	0.079 (15)	0.004 (9)	0.002 (11)	0.007 (9)
C11A	0.064 (15)	0.042 (11)	0.080 (16)	0.013 (11)	−0.012 (13)	−0.001 (11)
N12A	0.057 (11)	0.064 (11)	0.045 (9)	0.017 (10)	−0.008 (9)	0.004 (8)
C13A	0.036 (10)	0.049 (10)	0.059 (12)	0.006 (9)	−0.001 (10)	−0.002 (9)
N1B	0.027 (7)	0.032 (7)	0.045 (8)	−0.004 (6)	−0.013 (7)	0.007 (6)
C2B	0.033 (9)	0.031 (8)	0.047 (11)	0.003 (7)	0.009 (9)	−0.001 (7)
O2B	0.045 (8)	0.057 (8)	0.045 (8)	0.014 (7)	−0.010 (7)	0.013 (6)
C3B	0.034 (10)	0.040 (9)	0.067 (13)	0.012 (9)	0.002 (10)	0.003 (9)
C4B	0.050 (13)	0.053 (11)	0.052 (12)	0.020 (10)	0.024 (11)	0.003 (9)
C5B	0.052 (13)	0.051 (11)	0.039 (10)	0.000 (10)	0.004 (10)	0.002 (9)
C6B	0.038 (10)	0.028 (8)	0.048 (10)	0.004 (8)	−0.004 (9)	0.003 (7)
C7B	0.048 (12)	0.043 (10)	0.046 (11)	−0.001 (10)	−0.005 (10)	0.004 (8)
C8B	0.029 (10)	0.062 (13)	0.069 (14)	0.001 (10)	−0.011 (10)	0.018 (11)
C9B	0.028 (10)	0.051 (10)	0.062 (12)	0.011 (8)	0.008 (10)	0.013 (9)
C10B	0.036 (10)	0.051 (10)	0.038 (10)	0.004 (9)	0.002 (9)	0.001 (8)
C11B	0.044 (11)	0.047 (10)	0.069 (13)	0.001 (10)	0.011 (11)	0.004 (10)
N12B	0.058 (11)	0.034 (8)	0.055 (10)	0.002 (8)	0.001 (9)	0.010 (7)
C13B	0.052 (12)	0.050 (11)	0.052 (12)	0.000 (10)	−0.004 (11)	0.008 (9)
I1C	0.0626 (9)	0.0475 (7)	0.0637 (9)	−0.0061 (7)	0.0073 (8)	−0.0098 (6)
I2C	0.0453 (7)	0.0509 (7)	0.0563 (8)	0.0002 (6)	−0.0029 (6)	0.0068 (6)
I3C	0.0513 (8)	0.0590 (7)	0.0554 (7)	0.0056 (7)	0.0041 (7)	0.0013 (6)
I1D	0.0784 (12)	0.0573 (8)	0.0732 (10)	0.0029 (8)	0.0048 (9)	0.0009 (7)
I2D	0.0519 (8)	0.0515 (7)	0.0755 (10)	0.0039 (6)	−0.0053 (8)	−0.0073 (7)
I3D	0.0452 (7)	0.0470 (6)	0.0627 (8)	−0.0041 (6)	−0.0073 (7)	−0.0021 (6)
I1E	0.0604 (8)	0.0431 (6)	0.0554 (7)	−0.0065 (6)	−0.0110 (7)	−0.0002 (6)

Geometric parameters (Å, º)

N1A—C2A	1.36 (2)	N1B—C10B	1.48 (2)
N1A—C6A	1.39 (3)	C2B—O2B	1.28 (2)
N1A—C10A	1.48 (2)	C2B—C3B	1.41 (3)
C2A—O2A	1.30 (3)	O2B—H2	1.2242
C2A—C3A	1.39 (3)	C3B—C4B	1.36 (3)
O2A—H2	1.2263	C3B—H3B	0.9300
C3A—C4A	1.32 (3)	C4B—C5B	1.39 (3)
C3A—H3A	0.9300	C4B—H4B	0.9300
C4A—C5A	1.39 (3)	C5B—C6B	1.40 (3)
C4A—H4A	0.9300	C5B—H5B	0.9300
C5A—C6A	1.36 (3)	C6B—C7B	1.49 (3)
C5A—H5A	0.9300	C7B—C8B	1.51 (3)
C6A—C7A	1.51 (3)	C7B—C13B	1.52 (3)
C7A—C8A	1.48 (3)	C7B—H7B	0.9800
C7A—C13A	1.53 (3)	C8B—C9B	1.55 (3)
C7A—H7A	0.9800	C8B—H8B1	0.9700
C8A—C9A	1.51 (3)	C8B—H8B2	0.9700
C8A—H8A1	0.9700	C9B—C11B	1.51 (3)
C8A—H8A2	0.9700	C9B—C10B	1.52 (3)
C9A—C10A	1.51 (3)	C9B—H9B	0.9800
C9A—C11A	1.53 (3)	C10B—H10C	0.9700
C9A—H9A	0.9800	C10B—H10D	0.9700
C10A—H10A	0.9700	C11B—N12B	1.51 (3)
C10A—H10B	0.9700	C11B—H11C	0.9700
C11A—N12A	1.47 (3)	C11B—H11D	0.9700
C11A—H11A	0.9700	N12B—C13B	1.50 (3)
C11A—H11B	0.9700	N12B—H12C	0.9700
N12A—C13A	1.50 (3)	N12B—H12D	0.9700
N12A—H12A	0.9700	C13B—H13C	0.9700
N12A—H12B	0.9700	C13B—H13D	0.9700
C13A—H13A	0.9700	I1C—I2C	2.917 (2)
C13A—H13B	0.9700	I2C—I3C	2.909 (2)
N1B—C6B	1.36 (2)	I1D—I2D	2.800 (3)
N1B—C2B	1.38 (2)
C2A—N1A—C6A	121.9 (17)	C6B—N1B—C10B	122.9 (15)
C2A—N1A—C10A	115.9 (18)	C2B—N1B—C10B	115.2 (15)
C6A—N1A—C10A	122.0 (15)	O2B—C2B—N1B	115.9 (17)
O2A—C2A—N1A	115.6 (19)	O2B—C2B—C3B	124.7 (18)
O2A—C2A—C3A	126.4 (19)	N1B—C2B—C3B	119.4 (18)
N1A—C2A—C3A	118 (2)	C2B—O2B—H2	115.3
C2A—O2A—H2	119.9	C4B—C3B—C2B	118.2 (19)
C4A—C3A—C2A	121 (2)	C4B—C3B—H3B	120.9
C4A—C3A—H3A	119.3	C2B—C3B—H3B	120.9
C2A—C3A—H3A	119.3	C3B—C4B—C5B	122.1 (19)
C3A—C4A—C5A	120 (2)	C3B—C4B—H4B	119.0
C3A—C4A—H4A	119.9	C5B—C4B—H4B	119.0
C5A—C4A—H4A	119.9	C4B—C5B—C6B	119.4 (19)
C6A—C5A—C4A	121 (2)	C4B—C5B—H5B	120.3
C6A—C5A—H5A	119.5	C6B—C5B—H5B	120.3
C4A—C5A—H5A	119.5	N1B—C6B—C5B	118.7 (17)
C5A—C6A—N1A	117.5 (18)	N1B—C6B—C7B	120.0 (17)
C5A—C6A—C7A	124 (2)	C5B—C6B—C7B	121.1 (17)
N1A—C6A—C7A	118.6 (17)	C6B—C7B—C8B	110.9 (16)
C8A—C7A—C6A	111.8 (19)	C6B—C7B—C13B	113.3 (18)
C8A—C7A—C13A	111.0 (18)	C8B—C7B—C13B	110.6 (18)
C6A—C7A—C13A	111.9 (16)	C6B—C7B—H7B	107.2
C8A—C7A—H7A	107.3	C8B—C7B—H7B	107.2
C6A—C7A—H7A	107.3	C13B—C7B—H7B	107.2
C13A—C7A—H7A	107.3	C7B—C8B—C9B	106.2 (17)
C7A—C8A—C9A	106.9 (17)	C7B—C8B—H8B1	110.5
C7A—C8A—H8A1	110.3	C9B—C8B—H8B1	110.5
C9A—C8A—H8A1	110.3	C7B—C8B—H8B2	110.5
C7A—C8A—H8A2	110.3	C9B—C8B—H8B2	110.5
C9A—C8A—H8A2	110.3	H8B1—C8B—H8B2	108.7
H8A1—C8A—H8A2	108.6	C11B—C9B—C10B	115.4 (18)
C8A—C9A—C10A	111 (2)	C11B—C9B—C8B	110.2 (18)
C8A—C9A—C11A	109.6 (18)	C10B—C9B—C8B	108.3 (16)
C10A—C9A—C11A	115 (2)	C11B—C9B—H9B	107.5
C8A—C9A—H9A	107.1	C10B—C9B—H9B	107.5
C10A—C9A—H9A	107.1	C8B—C9B—H9B	107.5
C11A—C9A—H9A	107.1	N1B—C10B—C9B	114.7 (15)
N1A—C10A—C9A	114.9 (18)	N1B—C10B—H10C	108.6
N1A—C10A—H10A	108.5	C9B—C10B—H10C	108.6
C9A—C10A—H10A	108.5	N1B—C10B—H10D	108.6
N1A—C10A—H10B	108.5	C9B—C10B—H10D	108.6
C9A—C10A—H10B	108.5	H10C—C10B—H10D	107.6
H10A—C10A—H10B	107.5	N12B—C11B—C9B	112.5 (17)
N12A—C11A—C9A	112.8 (18)	N12B—C11B—H11C	109.1
N12A—C11A—H11A	109.0	C9B—C11B—H11C	109.1
C9A—C11A—H11A	109.0	N12B—C11B—H11D	109.1
N12A—C11A—H11B	109.0	C9B—C11B—H11D	109.1
C9A—C11A—H11B	109.0	H11C—C11B—H11D	107.8
H11A—C11A—H11B	107.8	C13B—N12B—C11B	114.3 (17)
C11A—N12A—C13A	114.9 (18)	C13B—N12B—H12C	108.7
C11A—N12A—H12A	108.5	C11B—N12B—H12C	108.7
C13A—N12A—H12A	108.5	C13B—N12B—H12D	108.7
C11A—N12A—H12B	108.5	C11B—N12B—H12D	108.7
C13A—N12A—H12B	108.5	H12C—N12B—H12D	107.6
H12A—N12A—H12B	107.5	N12B—C13B—C7B	108.6 (16)
N12A—C13A—C7A	110.6 (17)	N12B—C13B—H13C	110.0
N12A—C13A—H13A	109.5	C7B—C13B—H13C	110.0
C7A—C13A—H13A	109.5	N12B—C13B—H13D	110.0
N12A—C13A—H13B	109.5	C7B—C13B—H13D	110.0
C7A—C13A—H13B	109.5	H13C—C13B—H13D	108.3
H13A—C13A—H13B	108.1	I3C—I2C—I1C	171.86 (7)
C6B—N1B—C2B	121.8 (16)
C6A—N1A—C2A—O2A	178.9 (16)	C6B—N1B—C2B—O2B	175.2 (16)
C10A—N1A—C2A—O2A	4 (2)	C10B—N1B—C2B—O2B	−2 (2)
C6A—N1A—C2A—C3A	−3 (3)	C6B—N1B—C2B—C3B	−6 (2)
C10A—N1A—C2A—C3A	−178.1 (19)	C10B—N1B—C2B—C3B	176.6 (17)
O2A—C2A—C3A—C4A	−179 (2)	O2B—C2B—C3B—C4B	−178 (2)
N1A—C2A—C3A—C4A	4 (3)	N1B—C2B—C3B—C4B	3 (3)
C2A—C3A—C4A—C5A	−3 (4)	C2B—C3B—C4B—C5B	0 (3)
C3A—C4A—C5A—C6A	3 (4)	C3B—C4B—C5B—C6B	0 (3)
C4A—C5A—C6A—N1A	−3 (3)	C2B—N1B—C6B—C5B	6 (2)
C4A—C5A—C6A—C7A	179 (2)	C10B—N1B—C6B—C5B	−177.2 (17)
C2A—N1A—C6A—C5A	3 (3)	C2B—N1B—C6B—C7B	−178.4 (16)
C10A—N1A—C6A—C5A	177 (2)	C10B—N1B—C6B—C7B	−2 (3)
C2A—N1A—C6A—C7A	−179.1 (17)	C4B—C5B—C6B—N1B	−3 (3)
C10A—N1A—C6A—C7A	−5 (3)	C4B—C5B—C6B—C7B	−178.3 (19)
C5A—C6A—C7A—C8A	−151 (2)	N1B—C6B—C7B—C8B	29 (2)
N1A—C6A—C7A—C8A	32 (3)	C5B—C6B—C7B—C8B	−155.3 (18)
C5A—C6A—C7A—C13A	84 (3)	N1B—C6B—C7B—C13B	−96 (2)
N1A—C6A—C7A—C13A	−94 (2)	C5B—C6B—C7B—C13B	80 (2)
C6A—C7A—C8A—C9A	−60 (2)	C6B—C7B—C8B—C9B	−61 (2)
C13A—C7A—C8A—C9A	65 (2)	C13B—C7B—C8B—C9B	66 (2)
C7A—C8A—C9A—C10A	64 (2)	C7B—C8B—C9B—C11B	−61 (2)
C7A—C8A—C9A—C11A	−63 (2)	C7B—C8B—C9B—C10B	66 (2)
C2A—N1A—C10A—C9A	−176.8 (18)	C6B—N1B—C10B—C9B	8 (3)
C6A—N1A—C10A—C9A	8 (3)	C2B—N1B—C10B—C9B	−175.2 (16)
C8A—C9A—C10A—N1A	−38 (3)	C11B—C9B—C10B—N1B	84 (2)
C11A—C9A—C10A—N1A	86 (3)	C8B—C9B—C10B—N1B	−40 (2)
C8A—C9A—C11A—N12A	54 (2)	C10B—C9B—C11B—N12B	−70 (2)
C10A—C9A—C11A—N12A	−71 (3)	C8B—C9B—C11B—N12B	53 (2)
C9A—C11A—N12A—C13A	−46 (3)	C9B—C11B—N12B—C13B	−49 (2)
C11A—N12A—C13A—C7A	46 (2)	C11B—N12B—C13B—C7B	52 (2)
C8A—C7A—C13A—N12A	−56 (2)	C6B—C7B—C13B—N12B	64 (2)
C6A—C7A—C13A—N12A	69 (2)	C8B—C7B—C13B—N12B	−61 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2B—H2···O2A	1.22	1.23	2.451 (19)	180
N12A—H12A···I1E^i	0.97	2.62	3.506 (19)	152
N12A—H12B···I1E^ii	0.97	2.59	3.464 (17)	150
C11B—H11C···I1C^iii	0.97	3.01	3.76 (2)	135
N12B—H12C···I3D	0.97	2.69	3.573 (18)	152
N12B—H12D···I1C	0.97	2.88	3.553 (16)	128
N12B—H12D···I3D^iii	0.97	2.94	3.765 (16)	143

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

6-Oxidaniumylidene-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-11-ium bis(perchlorate) (12)

Crystal data

C11H16N2O^2+·2ClO4^−	Dx = 1.681 Mg m^−3
Mr = 391.16	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 1977 reflections
a = 8.0018 (13) Å	θ = 5.3–72.9°
b = 11.7602 (16) Å	µ = 4.29 mm^−1
c = 16.421 (2) Å	T = 130 K
V = 1545.3 (4) Å^3	Prism, red
Z = 4	0.1 × 0.08 × 0.08 mm
F(000) = 808

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	2361 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	1729 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.111
Detector resolution: 10.5357 pixels mm^-1	θmax = 67.5°, θmin = 4.6°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −13→13
Tmin = 0.397, Tmax = 1.000	l = −19→14
4345 measured reflections

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)] = 0.081	w = 1/[σ^2(Fo^2) + (0.0701P)^2 + 4.6425P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.240	(Δ/σ)max < 0.001
S = 1.25	Δρmax = 0.92 e Å^−3
2361 reflections	Δρmin = −0.55 e Å^−3
218 parameters	Absolute structure: Flack x determined using 490 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: 0.02 (4)

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
N1	0.5111 (15)	0.0629 (7)	0.9037 (5)	0.027 (2)
C2	0.5008 (18)	0.1693 (9)	0.9396 (7)	0.031 (2)
O2	0.4961 (15)	0.2548 (6)	0.8895 (5)	0.040 (2)
H2	0.4368	0.3067	0.9095	0.048*
C3	0.493 (2)	0.1730 (10)	1.0227 (7)	0.043 (3)
H3	0.4859	0.2446	1.0493	0.052*
C4	0.494 (2)	0.0784 (10)	1.0672 (7)	0.040 (3)
H4	0.4871	0.0840	1.1248	0.048*
C5	0.5056 (19)	−0.0278 (10)	1.0315 (7)	0.037 (3)
H5	0.5103	−0.0946	1.0641	0.044*
C6	0.5101 (19)	−0.0349 (9)	0.9472 (7)	0.033 (2)
C7	0.5224 (18)	−0.1491 (9)	0.9044 (7)	0.035 (3)
H7	0.5813	−0.2037	0.9412	0.042*
C8	0.6211 (19)	−0.1388 (11)	0.8260 (8)	0.040 (3)
H8A	0.6297	−0.2134	0.7984	0.048*
H8B	0.7352	−0.1101	0.8369	0.048*
C9	0.5217 (18)	−0.0529 (10)	0.7725 (7)	0.035 (3)
H9	0.5810	−0.0478	0.7190	0.042*
C10	0.5334 (17)	0.0636 (9)	0.8121 (7)	0.033 (3)
H10A	0.6440	0.0969	0.7992	0.039*
H10B	0.4472	0.1136	0.7879	0.039*
C11	0.3465 (17)	−0.0921 (10)	0.7548 (7)	0.033 (3)
H11A	0.3508	−0.1626	0.7220	0.040*
H11B	0.2882	−0.0333	0.7223	0.040*
N12	0.2487 (13)	−0.1144 (9)	0.8324 (6)	0.033 (2)
H12A	0.1402	−0.1500	0.8186	0.039*
H12B	0.2258	−0.0414	0.8603	0.039*
C13	0.3466 (17)	−0.1926 (11)	0.8893 (9)	0.042 (3)
H13A	0.2868	−0.1987	0.9419	0.050*
H13B	0.3526	−0.2696	0.8651	0.050*
Cl1A	0.5132 (5)	0.5274 (2)	0.98398 (17)	0.0376 (7)
O1A	0.3918 (13)	0.4453 (7)	0.9562 (7)	0.057 (3)
O2A	0.4344 (14)	0.6157 (7)	1.0274 (6)	0.053 (3)
O3A	0.6355 (12)	0.4695 (7)	1.0351 (5)	0.040 (2)
O4A	0.5991 (16)	0.5717 (9)	0.9150 (6)	0.060 (3)
Cl1B	−0.0055 (5)	−0.3455 (2)	0.73580 (16)	0.0370 (7)
O1B	0.0349 (17)	−0.4631 (8)	0.7480 (7)	0.063 (3)
O2B	0.1165 (12)	−0.2916 (8)	0.6854 (6)	0.043 (2)
O3B	−0.1697 (13)	−0.3383 (10)	0.6976 (6)	0.057 (3)
O4B	−0.0117 (16)	−0.2881 (8)	0.8129 (5)	0.052 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.025 (5)	0.025 (4)	0.032 (4)	0.001 (5)	0.002 (5)	−0.004 (4)
C2	0.022 (5)	0.027 (5)	0.045 (6)	0.002 (7)	0.003 (7)	0.003 (5)
O2	0.053 (6)	0.021 (4)	0.046 (4)	0.000 (5)	0.003 (6)	−0.002 (3)
C3	0.061 (8)	0.027 (6)	0.042 (6)	0.013 (8)	−0.001 (9)	−0.004 (5)
C4	0.045 (8)	0.033 (6)	0.041 (6)	0.003 (7)	0.008 (8)	−0.012 (5)
C5	0.041 (7)	0.032 (6)	0.037 (6)	−0.009 (7)	−0.010 (7)	0.014 (5)
C6	0.033 (6)	0.028 (5)	0.037 (5)	−0.005 (7)	0.003 (7)	−0.001 (5)
C7	0.040 (8)	0.020 (5)	0.044 (6)	−0.008 (6)	−0.008 (7)	0.003 (5)
C8	0.046 (8)	0.024 (6)	0.050 (7)	0.008 (6)	0.001 (7)	0.001 (6)
C9	0.044 (8)	0.032 (6)	0.029 (5)	−0.001 (7)	0.003 (7)	−0.004 (4)
C10	0.039 (8)	0.023 (5)	0.036 (5)	−0.008 (5)	0.000 (6)	0.007 (5)
C11	0.048 (8)	0.021 (6)	0.030 (6)	0.001 (6)	−0.001 (6)	−0.006 (5)
N12	0.028 (5)	0.030 (5)	0.041 (6)	0.003 (5)	−0.013 (5)	0.005 (4)
C13	0.038 (8)	0.029 (7)	0.058 (8)	−0.012 (6)	−0.016 (7)	−0.007 (6)
Cl1A	0.0492 (18)	0.0224 (12)	0.0413 (13)	−0.0005 (15)	−0.0039 (18)	−0.0060 (11)
O1A	0.045 (6)	0.020 (4)	0.107 (9)	−0.001 (4)	−0.020 (6)	−0.022 (5)
O2A	0.078 (8)	0.026 (4)	0.053 (5)	0.006 (5)	0.009 (6)	−0.009 (4)
O3A	0.040 (5)	0.029 (4)	0.050 (5)	0.005 (4)	−0.017 (5)	0.010 (4)
O4A	0.094 (9)	0.047 (6)	0.037 (5)	0.026 (6)	0.015 (6)	0.011 (5)
Cl1B	0.0367 (15)	0.0338 (14)	0.0404 (13)	−0.0040 (16)	−0.0007 (18)	0.0036 (11)
O1B	0.091 (10)	0.024 (5)	0.075 (6)	−0.001 (6)	0.018 (7)	0.013 (4)
O2B	0.032 (5)	0.037 (5)	0.059 (6)	−0.002 (4)	0.007 (5)	0.016 (5)
O3B	0.040 (6)	0.068 (7)	0.062 (6)	−0.006 (6)	−0.012 (5)	−0.009 (6)
O4B	0.057 (6)	0.051 (5)	0.048 (4)	0.004 (7)	−0.003 (6)	0.000 (4)

Geometric parameters (Å, º)

N1—C6	1.354 (14)	C9—C10	1.520 (16)
N1—C2	1.385 (13)	C9—H9	1.0000
N1—C10	1.515 (13)	C10—H10A	0.9900
C2—O2	1.299 (13)	C10—H10B	0.9900
C2—C3	1.368 (16)	C11—N12	1.518 (15)
O2—H2	0.8400	C11—H11A	0.9900
C3—C4	1.331 (16)	C11—H11B	0.9900
C3—H3	0.9500	N12—C13	1.528 (16)
C4—C5	1.383 (16)	N12—H12A	0.9900
C4—H4	0.9500	N12—H12B	0.9900
C5—C6	1.388 (15)	C13—H13A	0.9900
C5—H5	0.9500	C13—H13B	0.9900
C6—C7	1.518 (15)	Cl1A—O2A	1.409 (9)
C7—C8	1.516 (18)	Cl1A—O4A	1.423 (11)
C7—C13	1.517 (18)	Cl1A—O1A	1.444 (10)
C7—H7	1.0000	Cl1A—O3A	1.458 (9)
C8—C9	1.556 (18)	Cl1B—O2B	1.428 (10)
C8—H8A	0.9900	Cl1B—O1B	1.434 (10)
C8—H8B	0.9900	Cl1B—O4B	1.435 (9)
C9—C11	1.504 (19)	Cl1B—O3B	1.459 (11)
C6—N1—C2	122.9 (9)	N1—C10—C9	114.3 (9)
C6—N1—C10	121.9 (9)	N1—C10—H10A	108.7
C2—N1—C10	115.1 (8)	C9—C10—H10A	108.7
O2—C2—C3	127.2 (10)	N1—C10—H10B	108.7
O2—C2—N1	115.6 (9)	C9—C10—H10B	108.7
C3—C2—N1	117.1 (10)	H10A—C10—H10B	107.6
C2—O2—H2	109.5	C9—C11—N12	111.8 (9)
C4—C3—C2	121.4 (11)	C9—C11—H11A	109.3
C4—C3—H3	119.3	N12—C11—H11A	109.3
C2—C3—H3	119.3	C9—C11—H11B	109.3
C3—C4—C5	121.6 (11)	N12—C11—H11B	109.3
C3—C4—H4	119.2	H11A—C11—H11B	107.9
C5—C4—H4	119.2	C11—N12—C13	110.7 (10)
C4—C5—C6	118.6 (10)	C11—N12—H12A	109.5
C4—C5—H5	120.7	C13—N12—H12A	109.5
C6—C5—H5	120.7	C11—N12—H12B	109.5
N1—C6—C5	118.4 (10)	C13—N12—H12B	109.5
N1—C6—C7	120.5 (9)	H12A—N12—H12B	108.1
C5—C6—C7	121.1 (10)	C7—C13—N12	111.9 (10)
C8—C7—C13	111.8 (11)	C7—C13—H13A	109.2
C8—C7—C6	110.8 (10)	N12—C13—H13A	109.2
C13—C7—C6	108.3 (12)	C7—C13—H13B	109.2
C8—C7—H7	108.6	N12—C13—H13B	109.2
C13—C7—H7	108.6	H13A—C13—H13B	107.9
C6—C7—H7	108.6	O2A—Cl1A—O4A	110.4 (6)
C7—C8—C9	105.4 (11)	O2A—Cl1A—O1A	110.6 (7)
C7—C8—H8A	110.7	O4A—Cl1A—O1A	108.6 (7)
C9—C8—H8A	110.7	O2A—Cl1A—O3A	110.7 (6)
C7—C8—H8B	110.7	O4A—Cl1A—O3A	107.7 (7)
C9—C8—H8B	110.7	O1A—Cl1A—O3A	108.7 (6)
H8A—C8—H8B	108.8	O2B—Cl1B—O1B	110.8 (7)
C11—C9—C10	114.6 (11)	O2B—Cl1B—O4B	109.0 (6)
C11—C9—C8	112.8 (11)	O1B—Cl1B—O4B	109.8 (6)
C10—C9—C8	108.2 (10)	O2B—Cl1B—O3B	109.9 (6)
C11—C9—H9	106.9	O1B—Cl1B—O3B	108.6 (7)
C10—C9—H9	106.9	O4B—Cl1B—O3B	108.7 (7)
C8—C9—H9	106.9
C6—N1—C2—O2	−177.2 (14)	N1—C6—C7—C13	−93.2 (15)
C10—N1—C2—O2	6.2 (18)	C5—C6—C7—C13	89.8 (17)
C6—N1—C2—C3	1 (2)	C13—C7—C8—C9	60.1 (13)
C10—N1—C2—C3	−175.4 (14)	C6—C7—C8—C9	−60.8 (14)
O2—C2—C3—C4	178.1 (16)	C7—C8—C9—C11	−59.7 (12)
N1—C2—C3—C4	0 (3)	C7—C8—C9—C10	68.1 (13)
C2—C3—C4—C5	1 (3)	C6—N1—C10—C9	10.9 (19)
C3—C4—C5—C6	−2 (3)	C2—N1—C10—C9	−172.4 (12)
C2—N1—C6—C5	−3 (2)	C11—C9—C10—N1	83.6 (14)
C10—N1—C6—C5	173.7 (13)	C8—C9—C10—N1	−43.1 (15)
C2—N1—C6—C7	−179.7 (14)	C10—C9—C11—N12	−67.3 (13)
C10—N1—C6—C7	−3 (2)	C8—C9—C11—N12	57.1 (13)
C4—C5—C6—N1	3 (2)	C9—C11—N12—C13	−51.3 (13)
C4—C5—C6—C7	−179.9 (14)	C8—C7—C13—N12	−59.4 (14)
N1—C6—C7—C8	29.7 (18)	C6—C7—C13—N12	63.0 (13)
C5—C6—C7—C8	−147.2 (14)	C11—N12—C13—C7	52.4 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1A	0.84	1.84	2.629 (12)	157
C3—H3···O2B^i	0.95	2.44	3.138 (15)	130
C5—H5···O4B^ii	0.95	2.45	3.351 (13)	158
C10—H10A···O2B^iii	0.99	2.34	3.278 (16)	159
C10—H10B···O3B^iv	0.99	2.30	3.135 (17)	141
C11—H11A···O2^v	0.99	2.41	3.232 (14)	140
C11—H11A···O2B	0.99	2.48	3.192 (16)	128
N12—H12A···O4B	0.99	2.03	2.935 (15)	151
N12—H12B···N1	0.99	2.69	3.182 (15)	111
N12—H12B···O3A^vi	0.99	2.05	2.909 (14)	144
N12—H12B···O3B^iv	0.99	2.61	3.344 (15)	131

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

6-Oxidaniumylidene-7,11-diazatricyclo[7.3.1.0^{{2,7}]trideca-2,4-dien-11-ium dichloride trihydrate (13)}

Crystal data

C11H16N2O^2+·2Cl^−·3H2O	F(000) = 336
Mr = 317.20	Dx = 1.331 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.3551 (3) Å	Cell parameters from 1986 reflections
b = 16.5198 (5) Å	θ = 3.4–25.8°
c = 7.4476 (3) Å	µ = 0.42 mm^−1
β = 119.027 (6)°	T = 295 K
V = 791.25 (7) Å^3	Prism, colourless
Z = 2	0.4 × 0.15 × 0.15 mm

Data collection

Agilent Xcalibur Eos diffractometer	2643 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2403 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 16.2413 pixels mm^-1	θmax = 26.4°, θmin = 3.4°
ω scan	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −20→20
Tmin = 0.942, Tmax = 1.000	l = −8→9
4851 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 0.0216P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.14 e Å^−3
2643 reflections	Δρmin = −0.16 e Å^−3
210 parameters	Absolute structure: Flack x determined using 901 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
7 restraints	Absolute structure parameter: −0.01 (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
N1	0.1622 (3)	0.50156 (14)	0.5201 (3)	0.0306 (5)
C2	0.3236 (4)	0.54985 (17)	0.5487 (4)	0.0337 (6)
O2	0.5090 (3)	0.52106 (14)	0.6756 (3)	0.0458 (5)
H2	0.602 (8)	0.557 (3)	0.687 (8)	0.094 (15)*
C3	0.2874 (5)	0.62279 (19)	0.4450 (5)	0.0425 (7)
H3	0.3980	0.6547	0.4598	0.051*
C4	0.0886 (6)	0.64711 (19)	0.3216 (5)	0.0485 (8)
H4	0.0627	0.6956	0.2500	0.058*
C5	−0.0755 (5)	0.60008 (19)	0.3019 (5)	0.0473 (8)
H5	−0.2112	0.6183	0.2217	0.057*
C6	−0.0397 (4)	0.52670 (19)	0.3997 (4)	0.0348 (6)
C7	−0.2131 (4)	0.4717 (2)	0.3732 (4)	0.0421 (7)
H7	−0.3287	0.5056	0.3589	0.050*
C8	−0.1506 (5)	0.4171 (2)	0.5573 (5)	0.0496 (8)
H8A	−0.2651	0.3821	0.5364	0.060*
H8B	−0.1099	0.4489	0.6804	0.060*
C9	0.0321 (5)	0.36725 (19)	0.5766 (4)	0.0429 (7)
H9	0.0728	0.3306	0.6934	0.051*
C10	0.2171 (4)	0.42232 (19)	0.6287 (4)	0.0372 (6)
H10A	0.2891	0.4322	0.7755	0.045*
H10B	0.3129	0.3943	0.5953	0.045*
C11	−0.0326 (5)	0.3147 (2)	0.3876 (5)	0.0490 (8)
H11A	0.0884	0.2866	0.3994	0.059*
H11B	−0.1314	0.2744	0.3813	0.059*
N12	−0.1284 (4)	0.36292 (18)	0.1948 (4)	0.0414 (6)
H12A	−0.037 (5)	0.389 (2)	0.179 (5)	0.044 (9)*
H12B	−0.195 (6)	0.330 (3)	0.103 (6)	0.064 (12)*
C13	−0.2899 (4)	0.4218 (2)	0.1774 (5)	0.0452 (8)
H13A	−0.320 (6)	0.457 (2)	0.060 (6)	0.059 (10)*
H13B	−0.404 (6)	0.393 (2)	0.162 (5)	0.045 (8)*
Cl1	0.22573 (12)	0.43250 (5)	0.13765 (12)	0.0490 (2)
Cl2	0.56129 (14)	0.24998 (6)	0.85358 (13)	0.0613 (3)
O1W	0.1898 (4)	0.59470 (17)	0.9000 (4)	0.0638 (7)
H1W1	0.227 (7)	0.559 (2)	0.991 (6)	0.077*
H1W2	0.268 (6)	0.629 (2)	0.985 (6)	0.077*
O2W	0.6926 (6)	0.7494 (2)	0.9064 (7)	0.0972 (10)
H2W1	0.630 (8)	0.745 (4)	0.974 (7)	0.117*
H2W2	0.699 (9)	0.7965 (19)	0.875 (9)	0.117*
O3W	0.7793 (4)	0.62434 (17)	0.7327 (4)	0.0635 (7)
H3W1	0.903 (4)	0.613 (3)	0.785 (6)	0.076*
H3W2	0.752 (6)	0.659 (2)	0.799 (6)	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0299 (11)	0.0332 (12)	0.0269 (11)	0.0021 (9)	0.0125 (9)	−0.0003 (9)
C2	0.0331 (14)	0.0351 (15)	0.0319 (14)	−0.0003 (13)	0.0149 (12)	−0.0030 (12)
O2	0.0297 (11)	0.0467 (13)	0.0519 (12)	−0.0036 (10)	0.0126 (10)	0.0029 (10)
C3	0.0503 (18)	0.0357 (16)	0.0418 (15)	−0.0043 (14)	0.0227 (14)	−0.0019 (14)
C4	0.063 (2)	0.0328 (16)	0.0454 (18)	0.0071 (15)	0.0224 (16)	0.0044 (14)
C5	0.0398 (17)	0.0468 (19)	0.0438 (16)	0.0155 (15)	0.0112 (13)	0.0038 (16)
C6	0.0286 (14)	0.0431 (16)	0.0308 (13)	0.0071 (13)	0.0130 (12)	−0.0037 (13)
C7	0.0281 (14)	0.0554 (19)	0.0435 (17)	0.0049 (14)	0.0180 (13)	−0.0028 (14)
C8	0.0428 (16)	0.070 (2)	0.0440 (16)	−0.0104 (17)	0.0275 (13)	−0.0047 (16)
C9	0.0417 (17)	0.0445 (18)	0.0374 (15)	−0.0084 (14)	0.0152 (13)	0.0087 (14)
C10	0.0336 (13)	0.0378 (16)	0.0351 (13)	0.0028 (13)	0.0126 (11)	0.0068 (13)
C11	0.0469 (18)	0.0415 (18)	0.0533 (18)	−0.0049 (15)	0.0202 (16)	0.0004 (15)
N12	0.0345 (13)	0.0485 (16)	0.0411 (14)	−0.0103 (13)	0.0183 (11)	−0.0101 (13)
C13	0.0269 (14)	0.059 (2)	0.0446 (17)	−0.0050 (15)	0.0131 (12)	−0.0044 (17)
Cl1	0.0497 (4)	0.0523 (5)	0.0591 (4)	−0.0031 (4)	0.0375 (4)	−0.0058 (4)
Cl2	0.0582 (5)	0.0504 (5)	0.0594 (5)	0.0066 (4)	0.0160 (4)	−0.0179 (4)
O1W	0.0672 (17)	0.0614 (18)	0.0577 (16)	−0.0083 (13)	0.0262 (14)	−0.0081 (13)
O2W	0.131 (3)	0.0474 (16)	0.154 (3)	0.007 (2)	0.102 (2)	0.001 (2)
O3W	0.0458 (13)	0.0596 (17)	0.0819 (19)	−0.0126 (13)	0.0284 (14)	−0.0159 (14)

Geometric parameters (Å, º)

N1—C2	1.359 (4)	C9—C11	1.519 (5)
N1—C6	1.374 (3)	C9—C10	1.522 (4)
N1—C10	1.488 (4)	C9—H9	0.9800
C2—O2	1.314 (3)	C10—H10A	0.9700
C2—C3	1.386 (4)	C10—H10B	0.9700
O2—H2	0.88 (6)	C11—N12	1.487 (4)
C3—C4	1.356 (5)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C5	1.382 (5)	N12—C13	1.491 (4)
C4—H4	0.9300	N12—H12A	0.86 (4)
C5—C6	1.372 (4)	N12—H12B	0.83 (4)
C5—H5	0.9300	C13—H13A	0.99 (4)
C6—C7	1.499 (4)	C13—H13B	0.92 (4)
C7—C8	1.515 (5)	O1W—H1W1	0.83 (2)
C7—C13	1.525 (4)	O1W—H1W2	0.83 (2)
C7—H7	0.9800	O2W—H2W1	0.83 (3)
C8—C9	1.522 (5)	O2W—H2W2	0.82 (3)
C8—H8A	0.9700	O3W—H3W1	0.82 (2)
C8—H8B	0.9700	O3W—H3W2	0.84 (2)
C2—N1—C6	120.7 (2)	C11—C9—C10	114.6 (3)
C2—N1—C10	116.4 (2)	C8—C9—C10	109.9 (3)
C6—N1—C10	122.9 (2)	C11—C9—H9	107.0
O2—C2—N1	115.0 (2)	C8—C9—H9	107.0
O2—C2—C3	124.6 (3)	C10—C9—H9	107.0
N1—C2—C3	120.4 (2)	N1—C10—C9	114.4 (2)
C2—O2—H2	108 (3)	N1—C10—H10A	108.7
C4—C3—C2	119.2 (3)	C9—C10—H10A	108.7
C4—C3—H3	120.4	N1—C10—H10B	108.7
C2—C3—H3	120.4	C9—C10—H10B	108.7
C3—C4—C5	120.3 (3)	H10A—C10—H10B	107.6
C3—C4—H4	119.9	N12—C11—C9	112.2 (3)
C5—C4—H4	119.9	N12—C11—H11A	109.2
C6—C5—C4	120.5 (3)	C9—C11—H11A	109.2
C6—C5—H5	119.8	N12—C11—H11B	109.2
C4—C5—H5	119.8	C9—C11—H11B	109.2
C5—C6—N1	118.8 (3)	H11A—C11—H11B	107.9
C5—C6—C7	122.3 (3)	C11—N12—C13	114.6 (3)
N1—C6—C7	118.9 (3)	C11—N12—H12A	112 (2)
C6—C7—C8	112.1 (2)	C13—N12—H12A	108 (2)
C6—C7—C13	110.5 (2)	C11—N12—H12B	105 (3)
C8—C7—C13	110.6 (3)	C13—N12—H12B	104 (3)
C6—C7—H7	107.8	H12A—N12—H12B	114 (4)
C8—C7—H7	107.8	N12—C13—C7	111.1 (2)
C13—C7—H7	107.8	N12—C13—H13A	107 (2)
C7—C8—C9	105.9 (2)	C7—C13—H13A	110 (2)
C7—C8—H8A	110.6	N12—C13—H13B	108 (2)
C9—C8—H8A	110.6	C7—C13—H13B	106.9 (19)
C7—C8—H8B	110.6	H13A—C13—H13B	113 (3)
C9—C8—H8B	110.6	H1W1—O1W—H1W2	91 (4)
H8A—C8—H8B	108.7	H2W1—O2W—H2W2	112 (6)
C11—C9—C8	110.8 (2)	H3W1—O3W—H3W2	114 (4)
C6—N1—C2—O2	176.5 (2)	C5—C6—C7—C13	82.5 (3)
C10—N1—C2—O2	−2.3 (3)	N1—C6—C7—C13	−95.1 (3)
C6—N1—C2—C3	−4.7 (4)	C6—C7—C8—C9	−60.1 (3)
C10—N1—C2—C3	176.5 (2)	C13—C7—C8—C9	63.7 (3)
O2—C2—C3—C4	−178.4 (3)	C7—C8—C9—C11	−62.4 (3)
N1—C2—C3—C4	2.9 (4)	C7—C8—C9—C10	65.4 (3)
C2—C3—C4—C5	0.8 (5)	C2—N1—C10—C9	−174.7 (2)
C3—C4—C5—C6	−2.8 (5)	C6—N1—C10—C9	6.6 (4)
C4—C5—C6—N1	1.1 (4)	C11—C9—C10—N1	86.2 (3)
C4—C5—C6—C7	−176.5 (3)	C8—C9—C10—N1	−39.4 (3)
C2—N1—C6—C5	2.7 (4)	C8—C9—C11—N12	54.9 (3)
C10—N1—C6—C5	−178.6 (3)	C10—C9—C11—N12	−70.2 (3)
C2—N1—C6—C7	−179.6 (2)	C9—C11—N12—C13	−47.3 (4)
C10—N1—C6—C7	−0.9 (4)	C11—N12—C13—C7	48.1 (4)
C5—C6—C7—C8	−153.6 (3)	C6—C7—C13—N12	67.6 (4)
N1—C6—C7—C8	28.8 (4)	C8—C7—C13—N12	−57.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3W	0.88 (6)	1.61 (6)	2.495 (4)	174 (5)
N12—H12A···Cl1	0.86 (4)	2.21 (4)	3.060 (3)	168 (3)
N12—H12B···Cl2^i	0.83 (4)	2.27 (5)	3.085 (3)	167 (4)
C13—H13B···Cl1^ii	0.92 (4)	2.72 (4)	3.433 (3)	135 (3)
O1W—H1W1···Cl1^iii	0.83 (2)	2.37 (3)	3.151 (3)	158 (4)
O1W—H1W2···Cl2^iv	0.83 (2)	2.36 (3)	3.169 (3)	164 (4)
O2W—H2W1···Cl2^iv	0.83 (3)	2.32 (3)	3.150 (3)	172 (6)
O2W—H2W2···Cl1^v	0.82 (3)	2.33 (3)	3.132 (4)	167 (6)
O3W—H3W1···O1W^vi	0.82 (2)	1.87 (3)	2.694 (4)	176 (5)
O3W—H3W2···O2W	0.84 (2)	1.85 (3)	2.674 (4)	168 (5)

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