N-Benzyl-N-[2-(N-benzyl-N′,N′,N′′,N′′-tetra­methyl­guanidinium­yl)eth­yl]-N′,N′,N′′,N′′-tetra­methyl­guanidinium dibromide 1.5-hydrate

The asymmetric unit of the hydrated title compound, C₂₆H₄₂N₆²⁺·2Br⁻·1.5H₂O, comprises one cation, two bromide anions and one and a half water mol­ecules, as one water molecule is fully occupied and the other is only half occupied [0.500 (6)]. Both bromide ions are disordered over two sites with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9). The C—N bond lengths in both central C₃N units of the bis­guanidinium ion range between 1.336 (3) and 1.349 (3) Å, indicating a degree of double-bond character. The central C atoms are bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charges are delocalized in both CN₃ planes. The crystal structure is stabilized by a three-dimensional network of O—H...O, O—H...Br and C—H...Br hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.040
• wR factor = 0.088
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom C24             has ADP max/min Ratio .....        3.2 prolat
PLAT220_ALERT_2_C Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        4.0 Ratio
PLAT222_ALERT_3_C Large Non-Solvent  H     Uiso(max)/Uiso(min) ...        4.9 Ratio
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.498 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600        104 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          1 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          5 Report
PLAT300_ALERT_4_G Atom Site Occupancy of *H29    is Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *H30    is Constrained at        0.5 Check
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =         71 Note
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   0.94) in Resd. #          2 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   0.52) in Resd. #          3 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   0.06) in Resd. #          4 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   0.48) in Resd. #          5 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms (   1.50) in Resd. #          7 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C24     ..       2.95 Ang.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          5 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         96 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  17 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
  11 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Synthesis and crystallization

The title compound was obtained by reaction of N,N,N',N'-tetra­methyl- N''-[2-(N',N',N'',N''- tetra­methyl­guanidino)ethyl]­guanidine (Tiritiris & Kantlehner, 2012) with two equivalents of benzyl bromide in aceto­nitrile at room temperature in nearly qu­anti­tative yield. After evaporation of the solvent, the crude product was recrystallized from a saturated aceto­nitrile-water solution. After several days at 273 K, colorless single crystals suitable for X-ray analysis were obtained.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 The O-bound H atoms of the water molecules were located in a difference Fourier map and their bond lengths were restrained to 0.90 (1) Å using the DFIX command. The atoms Br1 and Br2 are disordered over two sets of sites (Br1A and Br1B; Br2A and Br2B) with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9) respectively. The atoms Br1A and Br1B were restrained to have similar anisotropic displacement parameters. The position of O2 is only half occupied, the site occupancy factor was refined and converged to 0.500 (6). The occupancy factors of H29 and H30 were fixed to 0.5 and their U_iso(H) set at to 0.050 Ų.

S3. Experimental

The title compound was obtained by reaction of N,N,N',N'-tetramethyl- N''-[2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012) with two equivalents of benzyl bromide in acetonitrile at room temperature in nearly quantitative yield. After evaporation of the solvent, the crude product was recrystallized from a saturated acetonitrile-water solution. After several days at 273 K, colorless single crystals suitable for X-ray analysis were obtained.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Atoms Br1 and Br2 are each disordered over two sites (Br1A and Br1B; Br2A and Br2B) with refined occupancy ratios of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9), respectively. The atoms Br1A and Br1B were restrained to have similar anisotropic displacement parameters. The position of O2 is only half occupied, the site occupancy factor was refined and converged to 0.500 (6). The occupancy factors of H29 and H30 were fixed to 0.5 and their U_iso(H) set at 0.050 Ų.

Structure description

By reaction of two equivalents of N,N,N',N'-tetramethylchloroformamidinium chloride (Tiritiris & Kantlehner, 2008a) with 1,2-diaminoethane, a bisguanidinium dichloride (Wittmann et al., 2000) has been obtained which, after treating with an aqueous sodium hydroxide solution, yields N,N,N',N'-tetramethyl- N''-[2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine (Tiritiris & Kantlehner, 2012). By alkylation of the free nitrogen atoms, various bisguanidinium salts can be prepared. The hydrated title salt presented here is the first alkylated bisguanidinium derivative in our series to have been structurally characterized. The asymmetric unit of the structure contains one cation, two bromide anions and two water molecules (Fig. 1). Br1 and Br2 are each disordered over two sites with refined occupancies of 0.938 (3):0.062 (3) and 0.520 (9):0.480 (9) respectively·The position of one water molecule (O1) is fully occupied while that of the second water solvate (O2) has a refined occupancy of [0.500 (6)], yielding a 1.5-hydrate salt. Prominent bond parameters in the bisguanidinium cation are: C1—N1 = 1.336 (3), C1—N2 = 1.336 (3), C1—N3 = 1.349 (3) Å and C15—N4 = 1.349 (3), C15—N5 = 1.339 (3), C15—N6 = 1.339 (3) Å, indicating partial double-bond character for all. The N—C1—N and N—C15—N angles range from 119.4 (2)° to 120.4 (2)°, indicating that the carbon centres C1 and C15 adopt nearly ideal trigonal–planar environments. The positive charges of the dication are completely delocalized in both CN₃ planes. The crystal structure analysis reveals that the C—N and C—C bond lengths in the dication are in very good agreement with the values obtained for the diprotonated salt 1,2-bis-[2N'-(1,1,3,3-tetramethylguanidinium)]ethane dichloride tetrahydrate (Wittmann et al., 2000). The crystal structure of the related N,N,N',N'-tetramethyl-N''- [2-(N',N',N'',N''- tetramethylguanidino)ethyl]guanidine, has also been reported (Tiritiris & Kantlehner, 2012).

The crystal structure is stabilized by a network of O—H···O, O—H···Br and C—H···Br hydrogen bonds, Table 1. O—H···O hydrogen bonds between the water molecules and O—H···Br hydrogen bonds between water molecules and bromide ions are observed, Fig. 2. In addition, C—H···Br hydrogen bonds form between the –N(CH₃)₂, –CH₂ and aromatic –CH groups of the cation and the bromide ions, forming a three-dimensional network, Fig. 3.

Computing details

Data collection: COLLECT (Hooft, 2004); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The structure of the title compound with displacement ellipsoids at the 50% probability level. All hydrogen atoms are omitted for the sake of clarity. Only the disordered bromine atoms with the major occupancy are shown.
	Fig. 2. O—H···O and O—H···Br hydrogen bonds (black dashed lines) in the crystal structure of the title compound (view along ac).
	Fig. 3. Molecular packing of the title compound. The O—H···O, O—H···Br and C—H···Br hydrogen bonds are depicted by black dashed lines (view along ac).

N-Benzyl-N-[2-(N-benzyl-N',N',N'',N''-tetramethylguanidiniumyl)ethyl]-N',N',N'',N''-tetramethylguanidinium dibromide 1.5-hydrate

Crystal data

C26H42N6^2+·2Br^−·1.5H2O	F(000) = 1300
Mr = 625.50	Dx = 1.417 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1957 (9) Å	Cell parameters from 5843 reflections
b = 7.9654 (5) Å	θ = 0.4–28.3°
c = 30.4821 (18) Å	µ = 2.80 mm^−1
β = 97.934 (4)°	T = 100 K
V = 2932.8 (3) Å^3	Block, colorless
Z = 4	0.35 × 0.26 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	7000 independent reflections
Radiation source: fine-focus sealed tube	5093 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ scans, and ω scans	θmax = 28.1°, θmin = 1.7°
Absorption correction: multi-scan (Blessing, 1995)	h = −16→16
Tmin = 0.455, Tmax = 0.705	k = −10→9
11867 measured reflections	l = −40→40

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: mixed
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0334P)^2 + 1.9458P] where P = (Fo^2 + 2Fc^2)/3
7000 reflections	(Δ/σ)max < 0.001
362 parameters	Δρmax = 0.59 e Å^−3
5 restraints	Δρmin = −0.51 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1A	0.61652 (3)	0.32199 (15)	0.09074 (2)	0.02821 (18)	0.938 (3)
Br1B	0.6107 (5)	0.3919 (18)	0.0962 (2)	0.02821 (18)	0.062 (3)
Br2A	0.08222 (13)	0.1353 (4)	0.08416 (14)	0.0282 (5)	0.520 (9)
Br2B	0.08977 (8)	0.1763 (3)	0.10105 (14)	0.0240 (5)	0.480 (9)
C1	0.35370 (16)	0.7762 (3)	0.08670 (6)	0.0131 (5)
N1	0.36249 (14)	0.9429 (2)	0.09049 (6)	0.0146 (4)
N2	0.39307 (14)	0.6969 (2)	0.05355 (6)	0.0152 (4)
N3	0.30713 (14)	0.6861 (2)	0.11675 (6)	0.0131 (4)
C2	0.37669 (19)	1.0285 (3)	0.13337 (7)	0.0187 (5)
H2A	0.3928	0.9456	0.1571	0.028*
H2B	0.3086	1.0890	0.1371	0.028*
H2C	0.4382	1.1084	0.1346	0.028*
C3	0.3532 (2)	1.0538 (3)	0.05186 (7)	0.0224 (5)
H3A	0.3354	0.9871	0.0248	0.034*
H3B	0.4236	1.1123	0.0512	0.034*
H3C	0.2944	1.1363	0.0537	0.034*
C4	0.49080 (18)	0.7544 (3)	0.03505 (7)	0.0234 (5)
H4A	0.5215	0.8537	0.0513	0.035*
H4B	0.4700	0.7830	0.0037	0.035*
H4C	0.5465	0.6649	0.0377	0.035*
C5	0.34310 (18)	0.5430 (3)	0.03370 (7)	0.0192 (5)
H5A	0.3905	0.4470	0.0435	0.029*
H5B	0.3354	0.5517	0.0013	0.029*
H5C	0.2699	0.5271	0.0429	0.029*
C6	0.35329 (18)	0.5204 (3)	0.13192 (7)	0.0156 (5)
H6A	0.4244	0.5016	0.1205	0.019*
H6B	0.3014	0.4302	0.1203	0.019*
C7	0.37139 (17)	0.5150 (3)	0.18194 (7)	0.0139 (5)
C8	0.30142 (17)	0.4218 (3)	0.20481 (7)	0.0148 (5)
H8	0.2453	0.3543	0.1888	0.018*
C9	0.31251 (18)	0.4262 (3)	0.25082 (7)	0.0166 (5)
H9	0.2646	0.3613	0.2661	0.020*
C10	0.39372 (18)	0.5255 (3)	0.27427 (7)	0.0178 (5)
H10	0.4000	0.5316	0.3056	0.021*
C11	0.46563 (19)	0.6157 (3)	0.25182 (8)	0.0209 (5)
H11	0.5224	0.6818	0.2678	0.025*
C12	0.45473 (18)	0.6095 (3)	0.20599 (7)	0.0186 (5)
H12	0.5049	0.6706	0.1908	0.022*
C13	0.20801 (17)	0.7456 (3)	0.13420 (7)	0.0137 (4)
H13A	0.1928	0.8635	0.1251	0.016*
H13B	0.2204	0.7414	0.1670	0.016*
C14	0.10851 (17)	0.6355 (3)	0.11665 (7)	0.0187 (5)
H14A	0.0905	0.6512	0.0842	0.022*
H14B	0.1278	0.5160	0.1223	0.022*
C15	−0.08422 (18)	0.7306 (3)	0.11457 (7)	0.0202 (5)
N4	0.01152 (14)	0.6780 (2)	0.13802 (5)	0.0158 (4)
N5	−0.11477 (16)	0.6733 (3)	0.07340 (6)	0.0301 (5)
N6	−0.15023 (15)	0.8373 (3)	0.13257 (6)	0.0196 (4)
C16	0.02466 (18)	0.6553 (3)	0.18648 (7)	0.0180 (5)
H16A	0.0436	0.7656	0.2005	0.022*
H16B	0.0886	0.5799	0.1950	0.022*
C17	−0.07320 (17)	0.5853 (3)	0.20581 (7)	0.0156 (5)
C18	−0.08041 (18)	0.6212 (3)	0.24996 (7)	0.0173 (5)
H18	−0.0277	0.6943	0.2659	0.021*
C19	−0.16346 (18)	0.5518 (3)	0.27109 (7)	0.0195 (5)
H19	−0.1663	0.5751	0.3015	0.023*
C20	−0.24237 (19)	0.4481 (3)	0.24770 (7)	0.0230 (5)
H20	−0.3000	0.4016	0.2619	0.028*
C21	−0.23666 (19)	0.4129 (3)	0.20374 (8)	0.0253 (6)
H21	−0.2910	0.3428	0.1876	0.030*
C22	−0.15173 (19)	0.4794 (3)	0.18294 (7)	0.0214 (5)
H22	−0.1474	0.4523	0.1529	0.026*
C23	−0.0885 (2)	0.5048 (4)	0.05929 (9)	0.0488 (9)
H23A	−0.0523	0.4414	0.0848	0.073*
H23B	−0.0386	0.5123	0.0368	0.073*
H23C	−0.1568	0.4475	0.0468	0.073*
C24	−0.1789 (2)	0.7764 (5)	0.03946 (8)	0.0523 (10)
H24A	−0.2551	0.7347	0.0340	0.078*
H24B	−0.1456	0.7705	0.0120	0.078*
H24C	−0.1789	0.8931	0.0496	0.078*
C25	−0.27108 (18)	0.8224 (3)	0.12385 (8)	0.0260 (6)
H25A	−0.2910	0.7196	0.1069	0.039*
H25B	−0.3018	0.9199	0.1068	0.039*
H25C	−0.3012	0.8176	0.1520	0.039*
C26	−0.10728 (19)	0.9705 (3)	0.16283 (8)	0.0248 (6)
H26A	−0.1106	0.9350	0.1934	0.037*
H26B	−0.1520	1.0720	0.1564	0.037*
H26C	−0.0303	0.9943	0.1591	0.037*
O1	0.1101 (2)	0.8214 (4)	0.02327 (11)	0.0675 (7)
H27	0.103 (4)	0.843 (5)	−0.0055 (4)	0.091 (17)*
H28	0.088 (3)	0.916 (3)	0.0345 (12)	0.070 (14)*
O2	0.8250 (3)	0.1418 (5)	0.05550 (12)	0.0313 (13)	0.500 (6)
H29	0.773 (3)	0.198 (7)	0.0678 (15)	0.050*	0.5
H30	0.885 (2)	0.150 (7)	0.0762 (13)	0.050*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.01796 (13)	0.0464 (5)	0.01941 (14)	−0.00219 (17)	−0.00051 (10)	−0.0025 (2)
Br1B	0.01796 (13)	0.0464 (5)	0.01941 (14)	−0.00219 (17)	−0.00051 (10)	−0.0025 (2)
Br2A	0.0256 (3)	0.0281 (6)	0.0315 (10)	0.0112 (3)	0.0065 (5)	0.0102 (7)
Br2B	0.0177 (3)	0.0254 (6)	0.0284 (10)	0.0038 (3)	0.0014 (4)	0.0068 (7)
C1	0.0094 (10)	0.0189 (12)	0.0102 (10)	−0.0001 (9)	−0.0013 (8)	0.0041 (9)
N1	0.0157 (9)	0.0169 (10)	0.0111 (8)	−0.0017 (8)	0.0012 (7)	0.0026 (8)
N2	0.0120 (9)	0.0228 (11)	0.0114 (8)	−0.0018 (8)	0.0037 (7)	−0.0028 (8)
N3	0.0115 (9)	0.0156 (10)	0.0129 (8)	0.0041 (8)	0.0047 (7)	0.0026 (8)
C2	0.0171 (11)	0.0213 (13)	0.0166 (11)	−0.0016 (10)	−0.0017 (9)	−0.0017 (10)
C3	0.0254 (13)	0.0223 (13)	0.0188 (12)	−0.0016 (11)	0.0006 (10)	0.0084 (10)
C4	0.0167 (11)	0.0382 (15)	0.0168 (11)	−0.0045 (11)	0.0070 (9)	−0.0015 (11)
C5	0.0169 (11)	0.0246 (13)	0.0159 (11)	−0.0004 (10)	0.0018 (9)	−0.0065 (10)
C6	0.0132 (10)	0.0173 (12)	0.0169 (11)	0.0019 (9)	0.0046 (9)	0.0010 (9)
C7	0.0112 (10)	0.0140 (11)	0.0160 (10)	0.0054 (9)	0.0004 (8)	0.0008 (9)
C8	0.0125 (10)	0.0133 (12)	0.0183 (11)	0.0011 (9)	0.0010 (9)	0.0010 (9)
C9	0.0137 (11)	0.0186 (12)	0.0182 (11)	−0.0014 (9)	0.0049 (9)	0.0040 (9)
C10	0.0180 (11)	0.0209 (13)	0.0141 (10)	0.0036 (10)	0.0006 (9)	0.0008 (10)
C11	0.0171 (11)	0.0221 (13)	0.0215 (11)	−0.0050 (10)	−0.0044 (9)	0.0034 (10)
C12	0.0138 (11)	0.0200 (12)	0.0219 (12)	−0.0010 (10)	0.0024 (9)	0.0073 (10)
C13	0.0133 (10)	0.0160 (11)	0.0126 (10)	0.0034 (9)	0.0043 (8)	0.0026 (9)
C14	0.0124 (10)	0.0281 (14)	0.0156 (11)	0.0027 (10)	0.0025 (9)	−0.0044 (10)
C15	0.0143 (11)	0.0340 (14)	0.0123 (10)	0.0045 (11)	0.0019 (9)	0.0025 (10)
N4	0.0100 (8)	0.0270 (11)	0.0105 (8)	0.0031 (8)	0.0019 (7)	0.0004 (8)
N5	0.0158 (10)	0.0607 (16)	0.0127 (9)	0.0124 (10)	−0.0019 (8)	−0.0083 (10)
N6	0.0116 (9)	0.0318 (12)	0.0153 (9)	0.0038 (9)	0.0019 (7)	−0.0015 (9)
C16	0.0119 (10)	0.0287 (14)	0.0125 (10)	−0.0006 (10)	−0.0013 (8)	0.0011 (10)
C17	0.0117 (10)	0.0179 (12)	0.0170 (11)	0.0039 (9)	0.0011 (8)	0.0030 (9)
C18	0.0158 (11)	0.0178 (12)	0.0175 (11)	0.0019 (10)	−0.0004 (9)	0.0015 (10)
C19	0.0210 (12)	0.0209 (13)	0.0173 (11)	0.0051 (10)	0.0056 (9)	0.0031 (10)
C20	0.0173 (12)	0.0276 (14)	0.0246 (12)	0.0005 (11)	0.0044 (10)	0.0110 (11)
C21	0.0183 (12)	0.0276 (14)	0.0279 (13)	−0.0070 (11)	−0.0042 (10)	0.0046 (11)
C22	0.0203 (12)	0.0285 (14)	0.0144 (11)	−0.0029 (11)	−0.0012 (9)	0.0001 (10)
C23	0.0229 (14)	0.087 (3)	0.0344 (16)	0.0087 (16)	−0.0034 (12)	−0.0379 (17)
C24	0.0231 (14)	0.118 (3)	0.0150 (12)	0.0198 (18)	−0.0010 (11)	0.0095 (16)
C25	0.0117 (11)	0.0438 (17)	0.0227 (12)	0.0056 (11)	0.0038 (9)	−0.0004 (12)
C26	0.0212 (12)	0.0340 (15)	0.0202 (12)	0.0023 (11)	0.0064 (10)	0.0007 (11)
O1	0.0614 (17)	0.0511 (18)	0.090 (2)	−0.0120 (14)	0.0107 (16)	0.0147 (17)
O2	0.027 (2)	0.029 (2)	0.036 (2)	0.0050 (17)	−0.0023 (16)	−0.0022 (17)

Geometric parameters (Å, º)

Br1A—Br1B	0.588 (14)	C14—H14A	0.9900
Br2A—Br2B	0.6061 (8)	C14—H14B	0.9900
C1—N1	1.336 (3)	C15—N4	1.349 (3)
C1—N2	1.336 (3)	C15—N5	1.339 (3)
C1—N3	1.349 (3)	C15—N6	1.339 (3)
N1—C2	1.463 (3)	N4—C16	1.475 (3)
N1—C3	1.464 (3)	N5—C23	1.459 (4)
N2—C4	1.461 (3)	N5—C24	1.460 (3)
N2—C5	1.463 (3)	N6—C26	1.455 (3)
N3—C13	1.465 (3)	N6—C25	1.466 (3)
N3—C6	1.484 (3)	C16—C17	1.509 (3)
C2—H2A	0.9800	C16—H16A	0.9900
C2—H2B	0.9800	C16—H16B	0.9900
C2—H2C	0.9800	C17—C22	1.389 (3)
C3—H3A	0.9800	C17—C18	1.390 (3)
C3—H3B	0.9800	C18—C19	1.388 (3)
C3—H3C	0.9800	C18—H18	0.9500
C4—H4A	0.9800	C19—C20	1.388 (3)
C4—H4B	0.9800	C19—H19	0.9500
C4—H4C	0.9800	C20—C21	1.380 (3)
C5—H5A	0.9800	C20—H20	0.9500
C5—H5B	0.9800	C21—C22	1.392 (3)
C5—H5C	0.9800	C21—H21	0.9500
C6—C7	1.511 (3)	C22—H22	0.9500
C6—H6A	0.9900	C23—H23A	0.9800
C6—H6B	0.9900	C23—H23B	0.9800
C7—C8	1.389 (3)	C23—H23C	0.9800
C7—C12	1.389 (3)	C24—H24A	0.9800
C8—C9	1.391 (3)	C24—H24B	0.9800
C8—H8	0.9500	C24—H24C	0.9800
C9—C10	1.386 (3)	C25—H25A	0.9800
C9—H9	0.9500	C25—H25B	0.9800
C10—C11	1.385 (3)	C25—H25C	0.9800
C10—H10	0.9500	C26—H26A	0.9800
C11—C12	1.386 (3)	C26—H26B	0.9800
C11—H11	0.9500	C26—H26C	0.9800
C12—H12	0.9500	O1—H27	0.89 (1)
C13—C14	1.532 (3)	O1—H28	0.89 (1)
C13—H13A	0.9900	O2—H29	0.89 (1)
C13—H13B	0.9900	O2—H30	0.90 (1)
C14—N4	1.467 (3)
N2—C1—N1	120.15 (19)	N4—C14—H14A	109.4
N2—C1—N3	119.4 (2)	C13—C14—H14A	109.4
N1—C1—N3	120.40 (19)	N4—C14—H14B	109.4
C1—N1—C2	122.59 (18)	C13—C14—H14B	109.4
C1—N1—C3	122.27 (18)	H14A—C14—H14B	108.0
C2—N1—C3	115.08 (18)	N5—C15—N6	119.7 (2)
C1—N2—C4	122.81 (19)	N5—C15—N4	120.0 (2)
C1—N2—C5	122.44 (18)	N6—C15—N4	120.4 (2)
C4—N2—C5	114.73 (18)	C15—N4—C14	121.91 (18)
C1—N3—C13	121.39 (18)	C15—N4—C16	122.37 (18)
C1—N3—C6	120.50 (17)	C14—N4—C16	115.70 (16)
C13—N3—C6	118.08 (17)	C15—N5—C23	123.1 (2)
N1—C2—H2A	109.5	C15—N5—C24	121.7 (2)
N1—C2—H2B	109.5	C23—N5—C24	115.2 (2)
H2A—C2—H2B	109.5	C15—N6—C26	122.57 (19)
N1—C2—H2C	109.5	C15—N6—C25	121.4 (2)
H2A—C2—H2C	109.5	C26—N6—C25	116.04 (19)
H2B—C2—H2C	109.5	N4—C16—C17	117.00 (17)
N1—C3—H3A	109.5	N4—C16—H16A	108.0
N1—C3—H3B	109.5	C17—C16—H16A	108.0
H3A—C3—H3B	109.5	N4—C16—H16B	108.0
N1—C3—H3C	109.5	C17—C16—H16B	108.0
H3A—C3—H3C	109.5	H16A—C16—H16B	107.3
H3B—C3—H3C	109.5	C22—C17—C18	118.6 (2)
N2—C4—H4A	109.5	C22—C17—C16	123.8 (2)
N2—C4—H4B	109.5	C18—C17—C16	117.45 (19)
H4A—C4—H4B	109.5	C19—C18—C17	121.0 (2)
N2—C4—H4C	109.5	C19—C18—H18	119.5
H4A—C4—H4C	109.5	C17—C18—H18	119.5
H4B—C4—H4C	109.5	C20—C19—C18	119.8 (2)
N2—C5—H5A	109.5	C20—C19—H19	120.1
N2—C5—H5B	109.5	C18—C19—H19	120.1
H5A—C5—H5B	109.5	C21—C20—C19	119.7 (2)
N2—C5—H5C	109.5	C21—C20—H20	120.2
H5A—C5—H5C	109.5	C19—C20—H20	120.2
H5B—C5—H5C	109.5	C20—C21—C22	120.3 (2)
N3—C6—C7	109.64 (17)	C20—C21—H21	119.8
N3—C6—H6A	109.7	C22—C21—H21	119.8
C7—C6—H6A	109.7	C17—C22—C21	120.5 (2)
N3—C6—H6B	109.7	C17—C22—H22	119.8
C7—C6—H6B	109.7	C21—C22—H22	119.8
H6A—C6—H6B	108.2	N5—C23—H23A	109.5
C8—C7—C12	118.7 (2)	N5—C23—H23B	109.5
C8—C7—C6	120.48 (19)	H23A—C23—H23B	109.5
C12—C7—C6	120.8 (2)	N5—C23—H23C	109.5
C7—C8—C9	120.8 (2)	H23A—C23—H23C	109.5
C7—C8—H8	119.6	H23B—C23—H23C	109.5
C9—C8—H8	119.6	N5—C24—H24A	109.5
C10—C9—C8	119.8 (2)	N5—C24—H24B	109.5
C10—C9—H9	120.1	H24A—C24—H24B	109.5
C8—C9—H9	120.1	N5—C24—H24C	109.5
C11—C10—C9	119.8 (2)	H24A—C24—H24C	109.5
C11—C10—H10	120.1	H24B—C24—H24C	109.5
C9—C10—H10	120.1	N6—C25—H25A	109.5
C10—C11—C12	120.0 (2)	N6—C25—H25B	109.5
C10—C11—H11	120.0	H25A—C25—H25B	109.5
C12—C11—H11	120.0	N6—C25—H25C	109.5
C11—C12—C7	120.8 (2)	H25A—C25—H25C	109.5
C11—C12—H12	119.6	H25B—C25—H25C	109.5
C7—C12—H12	119.6	N6—C26—H26A	109.5
N3—C13—C14	109.99 (18)	N6—C26—H26B	109.5
N3—C13—H13A	109.7	H26A—C26—H26B	109.5
C14—C13—H13A	109.7	N6—C26—H26C	109.5
N3—C13—H13B	109.7	H26A—C26—H26C	109.5
C14—C13—H13B	109.7	H26B—C26—H26C	109.5
H13A—C13—H13B	108.2	H27—O1—H28	103 (4)
N4—C14—C13	111.17 (18)	H29—O2—H30	102.8 (15)
N2—C1—N1—C2	−147.57 (19)	N5—C15—N4—C14	32.3 (3)
N3—C1—N1—C2	31.1 (3)	N6—C15—N4—C14	−149.1 (2)
N2—C1—N1—C3	35.5 (3)	N5—C15—N4—C16	−146.1 (2)
N3—C1—N1—C3	−145.9 (2)	N6—C15—N4—C16	32.5 (3)
N1—C1—N2—C4	32.9 (3)	C13—C14—N4—C15	120.6 (2)
N3—C1—N2—C4	−145.7 (2)	C13—C14—N4—C16	−61.0 (3)
N1—C1—N2—C5	−148.7 (2)	N6—C15—N5—C23	−146.0 (2)
N3—C1—N2—C5	32.6 (3)	N4—C15—N5—C23	32.6 (4)
N2—C1—N3—C13	−140.3 (2)	N6—C15—N5—C24	33.1 (4)
N1—C1—N3—C13	41.0 (3)	N4—C15—N5—C24	−148.3 (2)
N2—C1—N3—C6	37.6 (3)	N5—C15—N6—C26	−145.8 (2)
N1—C1—N3—C6	−141.07 (19)	N4—C15—N6—C26	35.6 (3)
C1—N3—C6—C7	129.2 (2)	N5—C15—N6—C25	36.3 (3)
C13—N3—C6—C7	−52.8 (2)	N4—C15—N6—C25	−142.3 (2)
N3—C6—C7—C8	106.4 (2)	C15—N4—C16—C17	37.8 (3)
N3—C6—C7—C12	−70.5 (2)	C14—N4—C16—C17	−140.7 (2)
C12—C7—C8—C9	1.7 (3)	N4—C16—C17—C22	28.2 (3)
C6—C7—C8—C9	−175.2 (2)	N4—C16—C17—C18	−156.0 (2)
C7—C8—C9—C10	0.5 (3)	C22—C17—C18—C19	0.7 (3)
C8—C9—C10—C11	−2.0 (3)	C16—C17—C18—C19	−175.4 (2)
C9—C10—C11—C12	1.4 (4)	C17—C18—C19—C20	−1.6 (3)
C10—C11—C12—C7	0.8 (4)	C18—C19—C20—C21	1.0 (3)
C8—C7—C12—C11	−2.3 (3)	C19—C20—C21—C22	0.6 (4)
C6—C7—C12—C11	174.6 (2)	C18—C17—C22—C21	0.9 (3)
C1—N3—C13—C14	110.1 (2)	C16—C17—C22—C21	176.7 (2)
C6—N3—C13—C14	−67.8 (2)	C20—C21—C22—C17	−1.5 (4)
N3—C13—C14—N4	172.62 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H27···O2^i	0.89 (1)	1.87 (2)	2.646 (2)	146 (1)
O1—H28···Br2A^ii	0.89 (1)	2.31 (2)	3.160 (2)	159 (1)
O1—H28···Br2B^ii	0.89 (1)	2.90 (2)	3.720 (2)	155 (1)
O2—H29···Br1A	0.89 (1)	2.34 (2)	3.230 (2)	170 (1)
O2—H29···Br1B	0.89 (1)	2.75 (2)	3.637 (2)	173 (1)
O2—H30···Br2A^iii	0.90 (1)	2.39 (2)	3.139 (2)	141 (1)
O2—H30···Br2B^iii	0.90 (1)	2.52 (2)	3.346 (2)	153 (1)
C2—H2B···Br2B^ii	0.98	2.83	3.694 (2)	148
C3—H3C···Br2A^ii	0.98	2.87	3.634 (2)	136
C4—H4C···Br1B	0.98	2.85	3.632 (2)	137
C6—H6A···Br1B	0.99	2.64	3.611 (2)	169
C13—H13A···Br2A^ii	0.99	2.76	3.697 (2)	159
C13—H13A···Br2B^ii	0.99	2.84	3.804 (2)	165
C14—H14B···Br2B	0.99	2.81	3.692 (2)	149
C21—H21···Br1B^iv	0.95	2.90	3.544 (2)	126
C23—H23A···Br2B	0.98	2.73	3.525 (2)	138
C25—H25A···Br1B^iv	0.98	2.87	3.770 (2)	153
C26—H26C···Br2B^ii	0.98	2.84	3.641 (2)	139

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