Bis[trans-dibromo(2,2-di­methylpropane-1,3-diamine-[kappa]²N,N')chromium(III)] dibromide hydrogen perchlorate hexahydrate

In the title compound, [CrBr₂(C₅H₁₄N₂)₂]₂Br₂·HClO₄·6H₂O, there are two independent Cr^III complex cations which are conformational isomers of each other. The Cr atoms lie respectively on a center of symmetry and on a mirror plane and have octahedral environments, coordinated by the N atoms of two 2,2-di­methylpropane-1,3-diamine ligands and by two Br atoms in trans positions. The Cr-N and Cr-Br bond lengths are in the ranges 2.078 (3)-2.089 (3) and 2.4495 (9)-2.5017 (9) Å, respectively. The crystal structure consists of two Cr^III complex cations, two Br^- anions, a (ClO₄)^- anion and an [H₁₃O₆]⁺ hydrogen-bonded cluster cation.

S1. Comment

2,2-Dimethyl-1,3-diaminopropane (Me₂tn) can coordinate to a central metal ion as a bidentate ligand, forming a six-membered chelate ring, similar to the situation for unsubstituted 1,3-diaminopropane (tn; House, 1986). In addition to the conformational isomerism resulting from the six-membered chelate rings, the [CrBr₂(tn/Me₂tn)₂]⁺ complex cation can exist as a cis or trans isomer. Although electronic absorption and IR spectra have been used to identify the geometrical structures of chromium(III) complexes (Choi et al., 2002; Poon & Pun, 1980), assignments based on spectral data are not always conclusive (Stearns & Armstrong, 1992). Furthermore, since the structural chemistry of complexes of the type [Cr^IIIL₄Br₂]X is rare (Lisgarten et al., 1990), we prepared the title complex, (I), which contains the [CrBr₂(Me₂tn)₂]⁺ cation, and determined its crystal structure by X-ray analysis.

The structure analysis of (I) revealed that the crystal contains two crystallographically independent Cr^III complex moieties. As atom Cr1 is located at a crystallographic center of symmetry, this Cr^III complex cation has a molecular C_i symmetry, while the other complex cation, containing atom Cr2, has molecular C_s symmetry; atoms Cr2, Br21, Br22, C22, C24, C25, C27, C29 and C30 atoms are located on a crystallographic mirror plane. It was found that in both complex cations, the two Br atoms are coordinated to the central Cr atom in a trans arrangement. The Cr—Br bond lengths [2.4495 (9)–2.5017 (9) Å] are close to the value found in trans-[CrBr₂(cyclam)₂]Br (cyclam is 1,4,8,11-tetraazacyclotetradecane; Lisgarten et al., 1990). The Cr—-N bond lengths are in the range 2.078 (3)–2.089 (3) Å, which are typical values for Cr^III—N(primary amine) bonds. All of the six-membered chelate rings formed by the Me₂tn ligand adopt chair conformations, but two complex cations were so-called conformational (C_i and C_s) isomers due to the relative conformation of the two Me₂tn chelate rings, as shown in Fig. 1.

As well as the complex cations, the asymmetric unit of (I) also contains a Br^- ion (Br3), a half ClO₄^- anion and three O atoms (O1, O2 and O3) corresponding to the hydrated water molecules. Owing to charge balance, a half equivalent amount of H⁺ per Cr^III complex cation should be included in the crystal. We suspected that such an H⁺ ion was trapped between atoms O1 and O1ⁱⁱⁱ [symmetry code: (iii) 1 - x, y, -z], because the O1···O1ⁱⁱⁱ distance was only 2.347 (9) Å, pointing to the existence of a strong hydrogen-bonding interaction between these atoms (Minkwitz et al., 1998). Since atom O1 is also involved in a hydrogen bond with both O2 and O3^iv [O1···O2 2.662 (7) Å and O1···O3^iv 2.667 (7) Å; symmetry code: (iv) 1/2 + x, 1/2 - y, z], the hydrated H⁺ cation in this crystal forms an [H₁₃O₆]⁺ cluster cation (Fig. 2). Although both Eigen-type and chain-like structures of [H₉O₄]⁺ clusters are often observed (Frank & Reiss, 1997; Hassaballa et al., 1998), the H-shaped [H₁₃O₆]⁺ cluster cation found in the crystal of (I) has,to our best knowledge, not been reported previously.

Hence, (I) can be formulated as (H₁₃O₆){trans-[CrBr₂(Me₂tn)₂]}₂Br₂(ClO₄). For help in visualizing the complete structure of this compound, a drawing containing an H₁₃O₆⁺ cluster cation and two conformational isomers of the Cr^III complex cation, together with two Br^- anions and a ClO₄^- anion, is illustrated in Fig. 2.

S2. Experimental

The starting material trans-[CrCl₂(Me₂tn)₂]ClO₄ was synthesized according to the literature method of House (1986). The complex trans-[CrCl₂(Me₂tn)₂]ClO₄ (1.0 g) and NaOH (1.0 g) were suspended in water (10 ml) and heated at 333 K for 15 min. HBr (48%, 10 ml) and HClO₄ (60%, 5 ml) were added to the mixture. The solution was concentrated at 333 K until green crystals appeared. The reaction mixture was then placed in an ice bath and the crystalline product which was deposited was filtered off, washed with cold 2-propanol and then diethyl ether. Recrystallization of the crude product from 0.5 M HBr solution afforded green crystals of (I) suitable for X-ray analysis.

S3. Refinement

The water H atoms were located from difference syntheses and refined as parts of rigid groups, with O—H = 0.90 Å and U_iso(H) = 0.044 Ų. The position of the H⁺ ion (H00) was fixed at the midpoint between the atoms O1 and O1(1 - x, y, -z). Other H atoms were placed geometrically and refined using a riding model, with N—H = 0.90 Å, C—H = 0.96 (for methyl H) or 0.97 Å (for methylene H), and U_iso(H) = 1.2U_iso(N or C). The H atoms of the methyl groups (C24, C25, C29 and C30) were treated as positionally disordered over two sites.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Cooperation & Rigaku, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Perspective views of the two crystallographically independent complex cations in (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1/2 - x, 1/2 - y, -z; (ii) x, -y, z.]
	Fig. 2. View of a complete set of ions in (I). [Symmetry codes: (i) 1/2 - x, 1/2 - y, -z; (ii) x, -y, z; (iii) 1 - x, y, -z; (iv) 1/2 + x, 1/2 - y, z.]

trans-Dibromobis(2,2-dimethyl-1,3-diaminopropane)chromium(III) Bromide Hemi(hydrogen perchlorate) Trihydrate

Crystal data

[CrBr2(C5H14N2)2]2Br2·HClO4·6H2O	F(000) = 2400
Mr = 1200.74	Dx = 1.731 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71069 Å
a = 22.3862 (8) Å	Cell parameters from 24876 reflections
b = 24.7393 (8) Å	θ = 1.6–27.5°
c = 8.3230 (3) Å	µ = 5.78 mm^−1
β = 91.624 (1)°	T = 293 K
V = 4607.6 (3) Å^3	Plate, green
Z = 8	0.32 × 0.32 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID Imaging Plate diffractometer	5320 independent reflections
Radiation source: fine-focus sealed tube	4188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 10.00 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
ω scans	h = −26→26
Absorption correction: multi-scan (Higashi, 1995)	k = −30→32
Tmin = 0.188, Tmax = 0.560	l = −10→10
20618 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 9.0033P] where P = (Fo^2 + 2Fc^2)/3
5320 reflections	(Δ/σ)max = 0.002
228 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.60 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)
Br3	0.29087 (2)	0.176534 (16)	0.50962 (4)	0.04806 (13)
Br11	0.19102 (2)	0.335225 (17)	−0.00718 (5)	0.05015 (13)
Br21	0.21757 (3)	0.0000	0.10304 (7)	0.05798 (18)
Br22	0.31308 (3)	0.0000	0.64692 (6)	0.05400 (17)
Cr1	0.2500	0.2500	0.0000	0.03191 (18)
Cr2	0.26574 (4)	0.0000	0.37796 (9)	0.03325 (18)
Cl	0.0000	0.16923 (8)	0.5000	0.0705 (5)
O1	0.4979 (2)	0.1581 (2)	0.1407 (6)	0.1096 (16)
O2	0.4230 (2)	0.2077 (2)	0.3351 (6)	0.1109 (16)
O3	0.0933 (2)	0.3843 (2)	0.2930 (6)	0.1143 (16)
O41	0.0122 (4)	0.1410 (4)	0.6354 (7)	0.201 (4)
O42	0.0445 (6)	0.2016 (5)	0.4612 (12)	0.318 (8)
N11	0.19109 (14)	0.21564 (14)	−0.1693 (3)	0.0415 (7)
H11M	0.1638	0.2410	−0.1963	0.049*
H11N	0.2120	0.2089	−0.2578	0.049*
N12	0.19988 (14)	0.22128 (13)	0.1883 (3)	0.0377 (7)
H12M	0.2250	0.2175	0.2739	0.047*
H12N	0.1738	0.2474	0.2130	0.047*
N21	0.32399 (15)	−0.05930 (13)	0.3001 (4)	0.0432 (7)
H21M	0.3167	−0.0894	0.3572	0.053*
H21N	0.3136	−0.0667	0.1972	0.053*
N22	0.20486 (15)	−0.05914 (13)	0.4460 (4)	0.0446 (7)
H22M	0.1816	−0.0665	0.3588	0.055*
H22N	0.2261	−0.0893	0.4680	0.055*
C11	0.15758 (19)	0.16518 (17)	−0.1308 (5)	0.0479 (10)
H11A	0.1857	0.1354	−0.1225	0.061*
H11B	0.1297	0.1573	−0.2191	0.061*
C12	0.12281 (18)	0.16832 (18)	0.0254 (5)	0.0477 (9)
C13	0.16552 (19)	0.17025 (16)	0.1717 (5)	0.0448 (9)
H13A	0.1427	0.1651	0.2677	0.057*
H13B	0.1934	0.1404	0.1649	0.057*
C14	0.07988 (19)	0.2160 (2)	0.0238 (6)	0.0610 (12)
H14A	0.1021	0.2491	0.0172	0.073*
H14B	0.0576	0.2159	0.1206	0.073*
H14C	0.0529	0.2132	−0.0675	0.073*
C15	0.0877 (2)	0.1150 (2)	0.0352 (7)	0.0693 (13)
H15A	0.0641	0.1152	0.1297	0.090*
H15B	0.1151	0.0852	0.0403	0.090*
H15C	0.0619	0.1114	−0.0584	0.090*
C21	0.38967 (19)	−0.05071 (17)	0.3070 (5)	0.0501 (10)
H21A	0.4087	−0.0816	0.2583	0.065*
H21B	0.4030	−0.0493	0.4188	0.065*
C22	0.4106 (3)	0.0000	0.2241 (7)	0.0453 (13)
C24	0.3906 (3)	0.0000	0.0467 (7)	0.0617 (17)
H24A	0.3478	0.0006	0.0384	0.075*	0.5
H24B	0.4052	−0.0320	−0.0043	0.075*	0.50
H24C	0.4064	0.0314	−0.0052	0.075*	0.50
C25	0.4793 (3)	0.0000	0.2378 (9)	0.0667 (19)
H25A	0.4917	−0.0006	0.3491	0.080*	0.5
H25B	0.4945	0.0320	0.1880	0.080*	0.50
H25C	0.4945	−0.0314	0.1847	0.080*	0.50
C27	0.1262 (3)	0.0000	0.5701 (7)	0.0495 (14)
C28	0.16419 (19)	−0.05075 (17)	0.5826 (5)	0.0500 (10)
H28A	0.1881	−0.0492	0.6816	0.066*
H28B	0.1379	−0.0818	0.5895	0.066*
C29	0.0869 (3)	0.0000	0.4162 (8)	0.0617 (17)
H29A	0.1118	0.0000	0.3242	0.075*
H29B	0.0621	0.0317	0.4141	0.075*	0.50
H29C	0.0621	−0.0317	0.4141	0.075*	0.50
C30	0.0858 (3)	0.0000	0.7148 (9)	0.071 (2)
H30A	0.1099	−0.0006	0.8120	0.083*	0.5
H30B	0.0606	−0.0314	0.7107	0.083*	0.50
H30C	0.0615	0.0320	0.7127	0.083*	0.50
H00	0.5000	0.1581	0.0000	0.044*
H01A	0.5313	0.1449	0.1884	0.044*
H01B	0.4810	0.1723	0.2281	0.044*
H02A	0.4405	0.2375	0.3768	0.044*
H02B	0.3923	0.1870	0.3665	0.044*
H03A	0.1308	0.3890	0.3327	0.044*
H03B	0.0890	0.3490	0.2657	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br3	0.0635 (3)	0.0428 (2)	0.0376 (2)	0.00513 (19)	−0.00295 (17)	−0.00615 (15)
Br11	0.0553 (3)	0.0492 (2)	0.0461 (2)	0.01554 (19)	0.00436 (18)	0.00421 (17)
Br21	0.0621 (4)	0.0722 (4)	0.0390 (3)	0.000	−0.0088 (3)	0.000
Br22	0.0600 (4)	0.0684 (4)	0.0333 (3)	0.000	−0.0032 (2)	0.000
Cr1	0.0350 (4)	0.0382 (4)	0.0225 (3)	0.0071 (3)	−0.0011 (3)	−0.0005 (3)
Cr2	0.0405 (4)	0.0301 (4)	0.0292 (4)	0.000	0.0011 (3)	0.000
Cl	0.0839 (13)	0.0729 (12)	0.0548 (9)	0.000	0.0051 (9)	0.000
O1	0.103 (4)	0.140 (4)	0.085 (3)	0.014 (3)	0.006 (3)	0.003 (3)
O2	0.107 (3)	0.120 (4)	0.107 (3)	−0.051 (3)	0.017 (3)	−0.021 (3)
O3	0.083 (3)	0.123 (4)	0.135 (4)	0.019 (3)	−0.024 (3)	−0.015 (3)
O41	0.229 (8)	0.272 (10)	0.100 (4)	0.049 (8)	−0.016 (5)	0.061 (5)
O42	0.378 (15)	0.376 (15)	0.209 (9)	−0.260 (13)	0.142 (10)	−0.129 (10)
N11	0.0428 (17)	0.0543 (19)	0.0273 (14)	0.0076 (15)	−0.0021 (12)	−0.0061 (13)
N12	0.0426 (17)	0.0448 (17)	0.0256 (13)	0.0050 (14)	0.0011 (12)	−0.0008 (12)
N21	0.0513 (19)	0.0370 (17)	0.0417 (16)	−0.0012 (15)	0.0080 (14)	−0.0012 (13)
N22	0.0498 (19)	0.0364 (17)	0.0478 (17)	0.0001 (15)	0.0044 (14)	0.0025 (14)
C11	0.045 (2)	0.055 (2)	0.043 (2)	−0.0019 (19)	−0.0074 (17)	−0.0087 (18)
C12	0.038 (2)	0.057 (3)	0.048 (2)	−0.0012 (19)	0.0007 (17)	0.0016 (18)
C13	0.048 (2)	0.047 (2)	0.0397 (19)	0.0021 (18)	0.0034 (17)	0.0055 (17)
C14	0.041 (2)	0.084 (3)	0.058 (3)	0.011 (2)	0.0035 (19)	−0.001 (2)
C15	0.058 (3)	0.072 (3)	0.078 (3)	−0.016 (3)	0.001 (2)	0.001 (3)
C21	0.050 (2)	0.051 (2)	0.050 (2)	0.011 (2)	0.0063 (18)	0.0009 (19)
C22	0.041 (3)	0.053 (3)	0.042 (3)	0.000	0.006 (2)	0.000
C24	0.066 (4)	0.080 (5)	0.039 (3)	0.000	0.015 (3)	0.000
C25	0.048 (4)	0.076 (5)	0.077 (5)	0.000	0.016 (3)	0.000
C27	0.041 (3)	0.056 (4)	0.052 (3)	0.000	0.010 (2)	0.000
C28	0.052 (2)	0.046 (2)	0.052 (2)	−0.004 (2)	0.0099 (18)	0.0080 (18)
C29	0.048 (4)	0.072 (5)	0.065 (4)	0.000	0.001 (3)	0.000
C30	0.058 (4)	0.084 (5)	0.072 (5)	0.000	0.016 (3)	0.000

Geometric parameters (Å, º)

Br11—Cr1	2.4876 (4)	C11—H11B	0.9700
Br21—Cr2	2.5017 (9)	C12—C14	1.522 (6)
Br22—Cr2	2.4495 (9)	C12—C13	1.527 (6)
Cr1—N12^i	2.078 (3)	C12—C15	1.539 (6)
Cr1—N12	2.078 (3)	C13—H13A	0.9700
Cr1—N11	2.084 (3)	C13—H13B	0.9700
Cr1—N11^i	2.084 (3)	C14—H14A	0.9600
Cr1—Br11^i	2.4876 (4)	C14—H14B	0.9600
Cr2—N21	2.078 (3)	C14—H14C	0.9600
Cr2—N21^ii	2.079 (3)	C15—H15A	0.9600
Cr2—N22	2.089 (3)	C15—H15B	0.9600
Cr2—N22^ii	2.089 (3)	C15—H15C	0.9600
Cl—O42	1.325 (8)	C21—C22	1.512 (5)
Cl—O42^iii	1.325 (8)	C21—H21A	0.9700
Cl—O41^iii	1.347 (6)	C21—H21B	0.9700
Cl—O41	1.348 (6)	C22—C21^ii	1.512 (5)
O1—H00	1.173	C22—C24	1.530 (8)
O1—H01A	0.899	C22—C25	1.539 (9)
O1—H01B	0.899	C24—H24A	0.9600
O2—H02A	0.899	C24—H24B	0.9600
O2—H02B	0.900	C24—H24C	0.9600
O3—H03A	0.902	C25—H25A	0.9600
O3—H03B	0.905	C25—H25B	0.9600
N11—C11	1.496 (5)	C25—H25C	0.9600
N11—H11M	0.9000	C27—C28	1.518 (5)
N11—H11N	0.9000	C27—C28^ii	1.518 (5)
N12—C13	1.483 (5)	C27—C30	1.527 (9)
N12—H12M	0.9000	C27—C29	1.534 (9)
N12—H12N	0.9000	C28—H28A	0.9700
N21—C21	1.485 (5)	C28—H28B	0.9700
N21—H21M	0.9000	C29—H29A	0.9600
N21—H21N	0.9000	C29—H29B	0.9600
N22—C28	1.491 (5)	C29—H29C	0.9600
N22—H22M	0.9000	C30—H30A	0.9600
N22—H22N	0.9000	C30—H30B	0.9600
C11—C12	1.536 (6)	C30—H30C	0.9600
C11—H11A	0.9700
N12^i—Cr1—N12	180.0	C14—C12—C11	111.5 (4)
N12^i—Cr1—N11	88.54 (12)	C13—C12—C11	110.8 (3)
N12—Cr1—N11	91.46 (12)	C14—C12—C15	110.0 (4)
N12^i—Cr1—N11^i	91.46 (12)	C13—C12—C15	107.1 (4)
N12—Cr1—N11^i	88.54 (12)	C11—C12—C15	105.9 (4)
N11—Cr1—N11^i	180.0	N12—C13—C12	114.4 (3)
N12^i—Cr1—Br11	89.41 (9)	N12—C13—H13A	108.7
N12—Cr1—Br11	90.59 (9)	C12—C13—H13A	108.7
N11—Cr1—Br11	90.24 (9)	N12—C13—H13B	108.7
N11^i—Cr1—Br11	89.76 (9)	C12—C13—H13B	108.7
N12^i—Cr1—Br11^i	90.59 (9)	H13A—C13—H13B	107.6
N12—Cr1—Br11^i	89.41 (9)	C12—C14—H14A	109.5
N11—Cr1—Br11^i	89.76 (9)	C12—C14—H14B	109.5
N11^i—Cr1—Br11^i	90.24 (9)	H14A—C14—H14B	109.5
Br11—Cr1—Br11^i	180.0	C12—C14—H14C	109.5
N21—Cr2—N21^ii	89.79 (18)	H14A—C14—H14C	109.5
N21—Cr2—N22	90.57 (13)	H14B—C14—H14C	109.5
N21^ii—Cr2—N22	177.29 (14)	C12—C15—H15A	109.5
N21—Cr2—N22^ii	177.29 (14)	C12—C15—H15B	109.5
N21^ii—Cr2—N22^ii	90.57 (13)	H15A—C15—H15B	109.5
N22—Cr2—N22^ii	88.94 (18)	C12—C15—H15C	109.5
N21—Cr2—Br22	91.47 (9)	H15A—C15—H15C	109.5
N21^ii—Cr2—Br22	91.47 (9)	H15B—C15—H15C	109.5
N22—Cr2—Br22	91.20 (10)	N21—C21—C22	114.8 (4)
N22^ii—Cr2—Br22	91.20 (10)	N21—C21—H21A	108.6
N21—Cr2—Br21	88.45 (9)	C22—C21—H21A	108.6
N21^ii—Cr2—Br21	88.45 (9)	N21—C21—H21B	108.6
N22—Cr2—Br21	88.87 (10)	C22—C21—H21B	108.6
N22^ii—Cr2—Br21	88.88 (10)	H21A—C21—H21B	107.5
Br22—Cr2—Br21	179.89 (4)	C21^ii—C22—C21	112.1 (5)
O42—Cl—O42^iii	105.6 (13)	C21^ii—C22—C24	110.8 (3)
O42—Cl—O41^iii	104.2 (5)	C21—C22—C24	110.8 (3)
O42^iii—Cl—O41^iii	112.5 (8)	C21^ii—C22—C25	106.7 (3)
O42—Cl—O41	112.5 (8)	C21—C22—C25	106.7 (3)
O42^iii—Cl—O41	104.2 (5)	C24—C22—C25	109.6 (5)
O41^iii—Cl—O41	117.5 (9)	C22—C24—H24A	109.5
H00—O1—H01A	112.6	C22—C24—H24B	109.5
H00—O1—H01B	146.7	H24A—C24—H24B	109.5
H01A—O1—H01B	98.5	C22—C24—H24C	109.5
H02A—O2—H02B	132.8	H24A—C24—H24C	109.5
H03A—O3—H03B	107.9	H24B—C24—H24C	109.5
C11—N11—Cr1	120.5 (2)	C22—C25—H25A	109.5
C11—N11—H11M	107.2	C22—C25—H25B	109.5
Cr1—N11—H11M	107.2	H25A—C25—H25B	109.5
C11—N11—H11N	107.2	C22—C25—H25C	109.5
Cr1—N11—H11N	107.2	H25A—C25—H25C	109.5
H11M—N11—H11N	106.8	H25B—C25—H25C	109.5
C13—N12—Cr1	120.7 (2)	C28—C27—C28^ii	111.6 (5)
C13—N12—H12M	107.2	C28—C27—C30	106.8 (3)
Cr1—N12—H12M	107.2	C28^ii—C27—C30	106.8 (3)
C13—N12—H12N	107.2	C28—C27—C29	111.4 (3)
Cr1—N12—H12N	107.2	C28^ii—C27—C29	111.4 (3)
H12M—N12—H12N	106.8	C30—C27—C29	108.6 (5)
C21—N21—Cr2	121.1 (2)	N22—C28—C27	114.5 (4)
C21—N21—H21M	107.1	N22—C28—H28A	108.6
Cr2—N21—H21M	107.1	C27—C28—H28A	108.6
C21—N21—H21N	107.1	N22—C28—H28B	108.6
Cr2—N21—H21N	107.1	C27—C28—H28B	108.6
H21M—N21—H21N	106.8	H28A—C28—H28B	107.6
C28—N22—Cr2	121.8 (3)	C27—C29—H29A	109.5
C28—N22—H22M	106.9	C27—C29—H29B	109.5
Cr2—N22—H22M	106.9	H29A—C29—H29B	109.5
C28—N22—H22N	106.9	C27—C29—H29C	109.5
Cr2—N22—H22N	106.9	H29A—C29—H29C	109.5
H22M—N22—H22N	106.7	H29B—C29—H29C	109.5
N11—C11—C12	114.1 (3)	C27—C30—H30A	109.5
N11—C11—H11A	108.7	C27—C30—H30B	109.5
C12—C11—H11A	108.7	H30A—C30—H30B	109.5
N11—C11—H11B	108.7	C27—C30—H30C	109.5
C12—C11—H11B	108.7	H30A—C30—H30C	109.5
H11A—C11—H11B	107.6	H30B—C30—H30C	109.5
C14—C12—C13	111.3 (4)
N12^i—Cr1—N11—C11	149.8 (3)	Cr1—N11—C11—C12	52.9 (4)
N12—Cr1—N11—C11	−30.2 (3)	N11—C11—C12—C14	55.7 (5)
Br11—Cr1—N11—C11	−120.8 (3)	N11—C11—C12—C13	−68.9 (4)
Br11^i—Cr1—N11—C11	59.2 (3)	N11—C11—C12—C15	175.3 (3)
N11—Cr1—N12—C13	30.6 (3)	Cr1—N12—C13—C12	−53.9 (4)
N11^i—Cr1—N12—C13	−149.4 (3)	C14—C12—C13—N12	−55.2 (5)
Br11—Cr1—N12—C13	120.8 (3)	C11—C12—C13—N12	69.5 (4)
Br11^i—Cr1—N12—C13	−59.2 (3)	C15—C12—C13—N12	−175.5 (4)
N21^ii—Cr2—N21—C21	33.2 (3)	Cr2—N21—C21—C22	−54.1 (4)
N22—Cr2—N21—C21	−149.5 (3)	N21—C21—C22—C21^ii	66.1 (6)
Br22—Cr2—N21—C21	−58.3 (3)	N21—C21—C22—C24	−58.2 (5)
Br21—Cr2—N21—C21	121.7 (3)	N21—C21—C22—C25	−177.4 (4)
N21—Cr2—N22—C28	149.5 (3)	Cr2—N22—C28—C27	54.6 (5)
N22^ii—Cr2—N22—C28	−33.2 (4)	C28^ii—C27—C28—N22	−66.4 (6)
Br22—Cr2—N22—C28	58.0 (3)	C30—C27—C28—N22	177.2 (4)
Br21—Cr2—N22—C28	−122.1 (3)	C29—C27—C28—N22	58.8 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11M···O2^i	0.90	2.57	3.438 (6)	163
N11—H11N···Br3^iv	0.90	2.77	3.661 (3)	169
N12—H12M···Br3	0.90	2.62	3.496 (3)	163
N12—H12N···Br3^v	0.90	3.06	3.567 (3)	117
N21—H21M···Br3^ii	0.90	2.58	3.475 (3)	177
N21—H21N···Br11^vi	0.90	2.90	3.580 (3)	134
N22—H22N···Br3^ii	0.90	2.62	3.516 (3)	176
O1—H00···O1^vii	1.17	1.17	2.347 (9)	180
O1—H01A···O3^viii	0.90	1.77	2.667 (7)	175
O1—H01B···O2	0.90	1.82	2.662 (7)	155
O2—H02A···O42^v	0.90	2.05	2.89 (1)	157
O2—H02B···Br3	0.90	2.61	3.420 (5)	150
O3—H03A···Br3^v	0.90	2.70	3.383 (5)	133
O3—H03A···Br22^v	0.90	3.02	3.575 (5)	121

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