Crystal structure of hexa-kis-(urea-κO)chromium(III) dichromate bromide monohydrate from synchrotron X-ray data.

The title bromide salt, [Cr{CO(NH2)2}6](Cr2O7)Br·H2O, is isotypic to the corresponding chloride salt. Within the complex cation, the Cr(III) atom is coordinated by six O atoms of six urea ligands, displaying a slightly distorted octa-hedral coordination environment. The Cr-O bond lengths involving the urea ligands are in the range 1.9534 (13)-1.9776 (12) Å. The Cr2O7 (2-) anion has a nearly staggered conformation, with a bridging angle of 130.26 (10)°. The individual components are arranged in rows extending parallel to [100]. The Br(-) anion links the complex cation, as well as the solvent water mol-ecule, through N-H⋯Br and O-H⋯Br hydrogen-bonding inter-actions. The supra-molecular architecture also includes N-H⋯O and O-H⋯O hydrogen bonding between urea N-H and water O-H donor groups and the O atoms of the Cr2O7 (2-) anion as acceptor atoms, leading to a three-dimensional network structure.

Chemical context

Counter-ionic species in coordination compounds play important roles in chemistry, pharmacy, mol­ecular assembly, biology and catalysis, as well as contributing significantly to environmental pollution; however, their binding characteristics have not received much recognition (Martínez-Máñez & Sancenón, 2003 ▸; Fabbrizzi & Poggi, 2013 ▸). The study of the anion or cation effect in octa­hedral n class="Chemical">metal complexes may be expected to yield a great variety of new structures and properties of both chemical and biological significance. Chromium is usually found in trivalent and hexa­valent oxidation states in soil, ground water and seawater (Cespon-Romero et al., 1996 ▸). CrIII is an essential element in mammals for maintaining efficient glucose, lipid and protein metabolism. On the other hand, CrVI is toxic and recognized as a carcinogen to humans and wildlife. The dichromate ion is environmentally important due to its high toxicity (Yusof & Malek, 2009 ▸) and its use in many industrial processes (Goyal et al., 2003 ▸). Recently, the ionic reactions between hexa­ureachromium(III) and inorganic oxoanions (such as Cr2O7 2− or CrO4 2−) in aqueous solution have been investigated. It was found that [Cr(urea)6]3+ is suitable to target these oxoanions (Bala et al., 2013 ▸). Previously, the crystal structure of [Cr(urea)6](Cr2O7)Cl·H2O has been reported (Bondar et al., 1984 ▸). This complex crystallizes in the monoclinic space group P2/n with four formula units in a cell of dimensions a = 13.782 (2), b = 10.393 (1), c = 17.794 (3) Å and β = 94. 86 (2)°. Within our broader study of CrIII complexes as industrial materials (Choi & Lee, 2009 ▸; Choi & Moon, 2014 ▸; Moon & Choi, 2015 ▸), we report herein the preparation and crystal structure of [Cr(urea)6](Cr2O7)Br·H2O, (I).

Structural commentary

In order to check if compound (I) is isotypic to [Cr(urea)6](n class="Species">Cr2O7)Cl·H2O investigated previously (Bondar et al., 1984 ▸), a single-crystal X-ray structure determination was performed on the basis of synchrotron data. Compound (I) consists of the isolated complex cation [Cr(urea)6]3+, together with Cr2O7 2− and Br− counter-ions and a solvent water mol­ecule. Comparison of the space-group type, metrics and the arrangement of the mol­ecular components reveal (I) to be isotypic to the corresponding chloride salt. An ellipsoid plot of the mol­ecular components of compound (I) is depicted in Fig. 1 ▸.

Figure 1

The mol­ecular structures of the components in compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

The CrIII ion is coordinated by six n class="Chemical">urea ligands through oxygen atoms with CrA—OA bond lengths ranging from 1.9534 (13) to 1.9776 (12) Å, and with OA—CrA—OA bond angles in the range 85.10 (5)–92.95 (5)°. The CrA—OA bond lengths involving the urea ligand are in good agreement with the value of 1.9630 (17) Å for [Cr(urea)6](BF4)3 (Górska et al., 2014 ▸). They are also comparable with the corresponding lengths determined for trans-[Cr(nic-O)2(cyclam)]ClO4 (cyclam = 1,4,8,11-tetra­aza­cyclo­tetra­decane; nic-O = O-coordinating nicotinate; Choi, 2009 ▸), cis-[Cr(ox)(cyclam)]ClO4 (ox = oxalate; Choi et al., 2004a ▸), cis-[Cr(acac)(cyclam)](ClO4)2·0.5H2O (acac = acetyl­acetonate; Subhan et al., 2011 ▸), cis-[Cr(ONO)2(cyclam)]NO2 (Choi et al., 2004b ▸) or cis-[Cr(edda)(acac)] (edda = ethyl­enedi­amine-N,N’-di­acetate; Choi et al., 2012 ▸). The trans O1A—Cr1A—O4A, O3A—Cr1A—O6A and O2A—Cr1A—O5A bond angles are 176.27 (5)°, 173.94 (5)°, and 175.89 (5)°, respectively. The bond lengths within the urea ligand are in the ranges of 1.263 (2)–1.276 (2) and 1.316 (2)–1.328 (2) Å for C=O and C—N bonds, respectively. The C=O bonds are slightly longer than that in free non-coordinating urea (Guth et al., 1980 ▸). The isolated Cr2O7 2− and Br− anions remain outside the coordination sphere of the cation.

It is of inter­est to compare the conformation of Cr2O7 2− with that found in other ionic n class="Chemical">crystals. In the structure of compound (I) it is in a nearly staggered conformation, whereas in K2Cr2O7, the tetra­hedral CrO4 groups are in an almost eclipsed conformation (Brandon & Brown, 1968 ▸). As expected, the two bridging CrB—OB bonds of 1.7643 (18) and 1.8011 (17) Å are longer than the terminal CrB—OB bonds that are in the range of 1.6014 (16)–1.6299 (14) Å. The Cr1B—O7B—Cr2B bridging angle in the complex anion is 130.26 (10)°. The OB—CrB—OB bond angles in the two tetra­hedral CrO4 groups are between 105.21 (8) and 110.98 (10)°, indicating slight angular distortions.

It is confirmed that the [Cr(urea)6]3+ moiety in compound (I) may be used as a potential receptor for n class="Species">Cr2O7 2− anions due to its high positive charge and the large number of hydrogen-bond donor groups of its six urea ligands.

Supra­molecular features

The individual mol­ecular or ionic components of (I) are arranged in rows extending parallel to [100]. The packing in the crystal structure of (I) involves not only n class="Chemical">hydrogen bonds of the type N—H⋯O between urea amino donor groups and the O acceptor atoms of carbonyl groups, the water mol­ecule, or the Cr2O7 2− anion, but also N—H⋯Br hydrogen bonding between the urea amino groups and the Br− anion (Table 1 ▸). O—H⋯Br inter­actions involving the water mol­ecule are also observed. All these inter­actions are responsible for the formation of an intricate three-dimensional hydrogen-bonded network in (I) (Fig. 2 ▸).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1AH1A1O2B i	0.87	2.42	3.051(3)	129
N1AH1A2Br1C ii	0.87	2.60	3.4031(18)	155
N2AH2A1O6A	0.87	2.20	2.890(2)	136
N2AH2A1O1W	0.87	2.58	3.230(3)	132
N2AH2A2Br1C ii	0.87	2.73	3.5121(17)	150
N3AH3A1O3A	0.87	2.23	2.866(2)	130
N3AH3A2O5B iii	0.87	2.21	2.972(2)	147
N4AH4A1Br1C	0.87	2.55	3.4070(18)	171
N4AH4A2O5B iii	0.87	2.11	2.900(2)	151
N5AH5A1O6B i	0.87	2.52	3.174(2)	133
N5AH5A2O3B iv	0.87	2.33	3.108(2)	150
N6AH6A1O4A	0.87	2.17	2.914(2)	143
N6AH6A2O1B iv	0.87	2.15	2.920(2)	147
N7AH7A1O2A	0.87	2.12	2.865(2)	143
N7AH7A2O4B v	0.87	2.24	3.092(2)	168
N8AH8A1O7B	0.87	2.03	2.883(2)	166
N8AH8A2O5B v	0.87	2.04	2.875(2)	162
N9AH9A1O1A	0.87	2.22	2.954(2)	141
N9AH9A2O6B iv	0.87	2.21	2.997(2)	150
N10AH10AO1B	0.87	2.29	3.028(2)	142
N10AH10BO4B iv	0.87	2.39	3.184(2)	151
N11AH11AO1W	0.87	2.04	2.892(3)	167
N11AH11BBr1C vi	0.87	2.57	3.4031(18)	162
N12AH12AO5A	0.87	2.27	2.982(2)	140
N12AH12AO2B	0.87	2.54	3.051(2)	118
N12AH12BBr1C vi	0.87	2.85	3.6242(18)	149
O1WH1O1Br1C	0.85(1)	2.51(1)	3.332(2)	163(3)
O1WH2O1O5B vii	0.84(1)	2.57(2)	3.315(3)	149(3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Figure 2

The crystal packing of compound (I), viewed perpendicular to the ac plane. Dashed lines represent hydrogen-bonding inter­actions of the types N—H⋯O (blue), N—H⋯Br (pink), O—H⋯O (red) and O—H⋯Br (black).

Synthesis and crystallization

All chemicals were reagent-grade materials and used without further purification. Chromium(III) trin class="Chemical">bromide hexa­hydrate was obtained from Aldrich Chemical Co. and used as supplied. [Cr(urea)6]Br3·3H2O was used as the starting material and was prepared according to literature procedures (Brauer, 1965 ▸), except that chromium(III) tribromide hexa­hydrate was used in place of chromium(III) trichloride hexa­hydrate (Flint & Palacio, 1979 ▸). A 0.5 g sample of [Cr(urea)6]Br3·3H2O was dissolved in 20 mL of water. Potassium dichromate (0.22 g), dissolved in 10 mL of water, was added to this solution. The mixture was refluxed at 353 K for 10 min and then cooled to room temperature. Green crystals of (I) suitable for X-ray structure analysis formed overnight. These were collected by filtration, washed with 2-propanol, and air dried. Yield: 65%. Elemental analysis calculated for [Cr{CO(NH2)2}6](Cr2O7)Br·H2O: C, 9.92; H, 3.61; N, 23.14%; found: C, 10.32; H, 3.08; N, 23.38%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. n class="Disease">H atoms bound to nitro­gen were placed at calculated positions and treated as riding on their parent atoms, with N—H = 0.87 Å and U iso(H) = 1.2U eq(N). H atoms of the solvent water mol­ecule were found from difference maps and refined with U iso(H) = 1.2U eq(O) and restrained to O—H = 0.84 (1) and H⋯H = 1.36 (2) Å.

Table 2

Experimental details

Crystal data
Chemical formula	[Cr(CH4N2O)6](Cr2O7)BrH2O
M r	726.30
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	243
a, b, c ()	13.774(3), 10.474(2), 18.123(4)
()	94.37(3)
V (3)	2607.0(9)
Z	4
Radiation type	Synchrotron, = 0.620
(mm1)	1.97
Crystal size (mm)	0.17 0.08 0.04
Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski Minor, 1997 ▸)
T min, T max	0.727, 0.920
No. of measured, independent and observed [I > 2(I)] reflections	27665, 7308, 5831
R int	0.036
(sin /)max (1)	0.694
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.031, 0.091, 1.04
No. of reflections	7308
No. of parameters	331
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	1.02, 1.25

Computer programs: PAL ADSC Quantum-210 ADX (Arvai Nielsen, 1983 ▸), HKL3000sm (Otwinowski Minor, 1997 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), DIAMOND (Putz Brandenburg, 2007 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015019258/wm5225sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019258/wm5225Isup2.hkl

CCDC reference: 1430688

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cr(CH4N2O)6](Cr2O7)Br·H2O	F(000) = 1460
Mr = 726.30	Dx = 1.850 Mg m−3
Monoclinic, P2/n	Synchrotron radiation, λ = 0.620 Å
a = 13.774 (3) Å	Cell parameters from 102484 reflections
b = 10.474 (2) Å	θ = 0.4–33.6°
c = 18.123 (4) Å	µ = 1.97 mm−1
β = 94.37 (3)°	T = 243 K
V = 2607.0 (9) Å3	Block, green
Z = 4	0.17 × 0.08 × 0.04 mm

ADSC Q210 CCD area-detector diffractometer	5831 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.036
ω scans	θmax = 25.5°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −19→19
Tmin = 0.727, Tmax = 0.920	k = −14→14
27665 measured reflections	l = −25→25
7308 independent reflections

Refinement on F2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0607P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
7308 reflections	Δρmax = 1.01 e Å−3
331 parameters	Δρmin = −1.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cr1A	0.48784 (2)	0.24358 (2)	0.73428 (2)	0.01814 (7)
O1A	0.40481 (9)	0.09045 (11)	0.72718 (6)	0.0269 (3)
N1A	0.33471 (14)	−0.09246 (16)	0.69010 (10)	0.0418 (4)
H1A1	0.3286	−0.1131	0.7360	0.050*
H1A2	0.3140	−0.1441	0.6547	0.050*
N2A	0.38377 (13)	0.04656 (16)	0.60403 (9)	0.0365 (4)
H2A1	0.4103	0.1185	0.5925	0.044*
H2A2	0.3627	−0.0062	0.5694	0.044*
C1A	0.37546 (13)	0.01753 (16)	0.67403 (9)	0.0251 (3)
O2A	0.58364 (9)	0.16617 (11)	0.67175 (6)	0.0247 (2)
N3A	0.61554 (13)	−0.03008 (15)	0.72164 (9)	0.0363 (4)
H3A1	0.5774	−0.0167	0.7569	0.044*
H3A2	0.6464	−0.1023	0.7194	0.044*
N4A	0.68354 (14)	0.03653 (17)	0.61675 (10)	0.0432 (4)
H4A1	0.6904	0.0939	0.5828	0.052*
H4A2	0.7140	−0.0360	0.6151	0.052*
C2A	0.62668 (13)	0.05977 (16)	0.67111 (9)	0.0247 (3)
O3A	0.55288 (9)	0.15949 (11)	0.82167 (6)	0.0242 (2)
N5A	0.58535 (13)	0.11285 (15)	0.94126 (8)	0.0351 (4)
H5A1	0.5743	0.0326	0.9316	0.042*
H5A2	0.6018	0.1370	0.9864	0.042*
N6A	0.59470 (13)	0.31974 (15)	0.90232 (9)	0.0352 (4)
H6A1	0.5899	0.3762	0.8670	0.042*
H6A2	0.6111	0.3434	0.9476	0.042*
C3A	0.57714 (12)	0.19830 (17)	0.88725 (9)	0.0228 (3)
O4A	0.56802 (9)	0.39845 (11)	0.74788 (6)	0.0244 (2)
N7A	0.66023 (14)	0.41622 (16)	0.64918 (10)	0.0432 (5)
H7A1	0.6546	0.3351	0.6395	0.052*
H7A2	0.6937	0.4649	0.6217	0.052*
N8A	0.62761 (13)	0.58826 (15)	0.72028 (9)	0.0366 (4)
H8A1	0.6004	0.6213	0.7576	0.044*
H8A2	0.6613	0.6363	0.6925	0.044*
C4A	0.61789 (12)	0.46555 (16)	0.70582 (9)	0.0228 (3)
O5A	0.39560 (9)	0.33272 (11)	0.79418 (6)	0.0268 (3)
N9A	0.34380 (13)	0.17981 (16)	0.87118 (9)	0.0365 (4)
H9A1	0.3558	0.1195	0.8401	0.044*
H9A2	0.3203	0.1609	0.9130	0.044*
N10A	0.34220 (13)	0.39063 (16)	0.90220 (9)	0.0394 (4)
H10A	0.3531	0.4702	0.8919	0.047*
H10B	0.3187	0.3706	0.9439	0.047*
C5A	0.36129 (12)	0.30050 (18)	0.85473 (9)	0.0249 (3)
O6A	0.42481 (9)	0.31007 (11)	0.64197 (6)	0.0267 (3)
N11A	0.38747 (13)	0.44107 (17)	0.54758 (9)	0.0410 (4)
H11A	0.4000	0.3802	0.5171	0.049*
H11B	0.3686	0.5155	0.5306	0.049*
N12A	0.37717 (14)	0.51221 (16)	0.66616 (9)	0.0407 (4)
H12A	0.3828	0.4985	0.7136	0.049*
H12B	0.3584	0.5866	0.6491	0.049*
C6A	0.39707 (13)	0.42046 (16)	0.62008 (9)	0.0263 (3)
Cr1B	0.43809 (2)	0.74013 (3)	0.86870 (2)	0.02751 (8)
Cr2B	0.67274 (2)	0.73371 (2)	0.89720 (2)	0.02405 (7)
O1B	0.42792 (12)	0.65095 (15)	0.93969 (8)	0.0452 (4)
O2B	0.36945 (13)	0.6882 (2)	0.79973 (9)	0.0586 (5)
O3B	0.41248 (13)	0.88526 (15)	0.88712 (10)	0.0553 (4)
O4B	0.69792 (12)	0.59234 (12)	0.92738 (9)	0.0425 (3)
O5B	0.75382 (11)	0.78025 (13)	0.84199 (8)	0.0350 (3)
O6B	0.66869 (12)	0.83207 (14)	0.96458 (8)	0.0446 (4)
O7B	0.56137 (12)	0.73256 (16)	0.84224 (9)	0.0475 (4)
Br1C	0.68438 (2)	0.24957 (2)	0.47474 (2)	0.03324 (7)
O1W	0.44307 (16)	0.2183 (3)	0.46645 (14)	0.0752 (7)
H1O1	0.5018 (9)	0.236 (3)	0.460 (2)	0.090*
H2O1	0.414 (2)	0.224 (3)	0.4242 (10)	0.090*

	U11	U22	U33	U12	U13	U23
Cr1A	0.02397 (14)	0.01721 (12)	0.01352 (12)	−0.00045 (9)	0.00324 (9)	0.00064 (8)
O1A	0.0347 (7)	0.0256 (6)	0.0205 (6)	−0.0087 (5)	0.0029 (5)	−0.0020 (4)
N1A	0.0600 (12)	0.0324 (9)	0.0328 (9)	−0.0201 (8)	0.0028 (8)	−0.0024 (7)
N2A	0.0584 (11)	0.0293 (8)	0.0217 (7)	−0.0092 (7)	0.0016 (7)	−0.0050 (6)
C1A	0.0267 (8)	0.0252 (8)	0.0233 (8)	−0.0013 (6)	0.0011 (6)	−0.0021 (6)
O2A	0.0324 (6)	0.0207 (5)	0.0219 (5)	0.0047 (5)	0.0082 (5)	0.0012 (4)
N3A	0.0517 (10)	0.0254 (7)	0.0334 (8)	0.0121 (7)	0.0141 (7)	0.0084 (6)
N4A	0.0590 (11)	0.0328 (8)	0.0412 (10)	0.0212 (8)	0.0266 (8)	0.0096 (7)
C2A	0.0294 (9)	0.0221 (7)	0.0225 (8)	0.0029 (6)	0.0015 (6)	−0.0001 (6)
O3A	0.0340 (7)	0.0222 (5)	0.0160 (5)	0.0008 (5)	−0.0004 (4)	0.0003 (4)
N5A	0.0553 (11)	0.0303 (8)	0.0189 (7)	0.0038 (7)	−0.0019 (7)	0.0039 (6)
N6A	0.0535 (10)	0.0297 (8)	0.0211 (7)	−0.0090 (7)	−0.0058 (7)	−0.0008 (6)
C3A	0.0228 (8)	0.0271 (8)	0.0185 (7)	0.0025 (6)	0.0020 (6)	0.0002 (6)
O4A	0.0318 (6)	0.0227 (6)	0.0195 (5)	−0.0069 (5)	0.0071 (5)	−0.0003 (4)
N7A	0.0638 (12)	0.0300 (8)	0.0403 (10)	−0.0118 (8)	0.0336 (9)	−0.0061 (7)
N8A	0.0521 (10)	0.0250 (7)	0.0352 (8)	−0.0146 (7)	0.0194 (8)	−0.0063 (6)
C4A	0.0260 (8)	0.0240 (7)	0.0186 (7)	−0.0051 (6)	0.0024 (6)	0.0000 (6)
O5A	0.0320 (7)	0.0264 (6)	0.0234 (6)	0.0031 (5)	0.0108 (5)	0.0025 (5)
N9A	0.0468 (10)	0.0337 (8)	0.0312 (8)	−0.0092 (7)	0.0179 (7)	0.0007 (7)
N10A	0.0522 (11)	0.0358 (9)	0.0330 (9)	0.0025 (8)	0.0224 (8)	−0.0046 (7)
C5A	0.0200 (8)	0.0314 (9)	0.0239 (8)	−0.0003 (6)	0.0060 (6)	−0.0002 (6)
O6A	0.0372 (7)	0.0231 (6)	0.0192 (5)	0.0041 (5)	−0.0018 (5)	0.0018 (4)
N11A	0.0637 (12)	0.0345 (9)	0.0242 (8)	0.0140 (8)	0.0005 (8)	0.0082 (7)
N12A	0.0614 (12)	0.0286 (8)	0.0307 (9)	0.0152 (8)	−0.0061 (8)	−0.0029 (6)
C6A	0.0281 (9)	0.0253 (8)	0.0248 (8)	0.0009 (7)	−0.0026 (7)	0.0024 (6)
Cr1B	0.03041 (16)	0.03174 (16)	0.02060 (14)	0.00408 (11)	0.00341 (11)	−0.00030 (10)
Cr2B	0.03046 (15)	0.02096 (13)	0.02202 (14)	0.00009 (10)	0.01038 (11)	−0.00170 (10)
O1B	0.0603 (10)	0.0450 (9)	0.0315 (7)	0.0022 (7)	0.0112 (7)	0.0076 (6)
O2B	0.0538 (11)	0.0844 (13)	0.0358 (9)	−0.0078 (10)	−0.0086 (7)	−0.0112 (9)
O3B	0.0664 (12)	0.0354 (8)	0.0655 (11)	0.0140 (8)	0.0136 (9)	0.0039 (8)
O4B	0.0544 (9)	0.0253 (7)	0.0493 (9)	0.0019 (6)	0.0139 (7)	0.0074 (6)
O5B	0.0439 (8)	0.0273 (6)	0.0364 (7)	−0.0072 (6)	0.0200 (6)	−0.0046 (5)
O6B	0.0658 (10)	0.0378 (8)	0.0321 (7)	−0.0006 (7)	0.0166 (7)	−0.0119 (6)
O7B	0.0365 (9)	0.0763 (12)	0.0306 (8)	0.0079 (7)	0.0076 (6)	−0.0056 (7)
Br1C	0.04246 (12)	0.02884 (10)	0.02779 (11)	0.00280 (7)	−0.00149 (8)	−0.00060 (6)
O1W	0.0493 (12)	0.0971 (16)	0.0789 (16)	−0.0032 (12)	0.0040 (11)	−0.0419 (14)

Cr1A—O6A	1.9534 (13)	N7A—H7A1	0.8700
Cr1A—O4A	1.9672 (12)	N7A—H7A2	0.8700
Cr1A—O3A	1.9674 (12)	N8A—C4A	1.316 (2)
Cr1A—O5A	1.9683 (12)	N8A—H8A1	0.8700
Cr1A—O1A	1.9685 (12)	N8A—H8A2	0.8700
Cr1A—O2A	1.9776 (12)	O5A—C5A	1.273 (2)
O1A—C1A	1.271 (2)	N9A—C5A	1.325 (3)
N1A—C1A	1.324 (2)	N9A—H9A1	0.8700
N1A—H1A1	0.8700	N9A—H9A2	0.8700
N1A—H1A2	0.8700	N10A—C5A	1.317 (2)
N2A—C1A	1.318 (2)	N10A—H10A	0.8700
N2A—H2A1	0.8700	N10A—H10B	0.8700
N2A—H2A2	0.8700	O6A—C6A	1.272 (2)
O2A—C2A	1.263 (2)	N11A—C6A	1.328 (2)
N3A—C2A	1.330 (2)	N11A—H11A	0.8700
N3A—H3A1	0.8700	N11A—H11B	0.8700
N3A—H3A2	0.8700	N12A—C6A	1.316 (2)
N4A—C2A	1.327 (2)	N12A—H12A	0.8700
N4A—H4A1	0.8700	N12A—H12B	0.8700
N4A—H4A2	0.8700	Cr1B—O3B	1.6014 (16)
O3A—C3A	1.2763 (19)	Cr1B—O2B	1.6036 (17)
N5A—C3A	1.325 (2)	Cr1B—O1B	1.6045 (15)
N5A—H5A1	0.8700	Cr1B—O7B	1.8011 (17)
N5A—H5A2	0.8700	Cr2B—O6B	1.6018 (14)
N6A—C3A	1.319 (2)	Cr2B—O4B	1.6071 (14)
N6A—H6A1	0.8700	Cr2B—O5B	1.6299 (14)
N6A—H6A2	0.8700	Cr2B—O7B	1.7643 (18)
O4A—C4A	1.2753 (19)	O1W—H1O1	0.847 (10)
N7A—C4A	1.324 (2)	O1W—H2O1	0.840 (10)
O6A—Cr1A—O4A	91.26 (5)	C4A—O4A—Cr1A	134.62 (11)
O6A—Cr1A—O3A	173.94 (5)	C4A—N7A—H7A1	120.0
O4A—Cr1A—O3A	92.95 (5)	C4A—N7A—H7A2	120.0
O6A—Cr1A—O5A	92.28 (5)	H7A1—N7A—H7A2	120.0
O4A—Cr1A—O5A	85.39 (5)	C4A—N8A—H8A1	120.0
O3A—Cr1A—O5A	92.40 (5)	C4A—N8A—H8A2	120.0
O6A—Cr1A—O1A	90.94 (5)	H8A1—N8A—H8A2	120.0
O4A—Cr1A—O1A	176.27 (5)	O4A—C4A—N8A	118.05 (15)
O3A—Cr1A—O1A	85.10 (5)	O4A—C4A—N7A	122.52 (15)
O5A—Cr1A—O1A	91.51 (5)	N8A—C4A—N7A	119.42 (16)
O6A—Cr1A—O2A	85.86 (5)	C5A—O5A—Cr1A	130.34 (11)
O4A—Cr1A—O2A	90.98 (5)	C5A—N9A—H9A1	120.0
O3A—Cr1A—O2A	89.71 (5)	C5A—N9A—H9A2	120.0
O5A—Cr1A—O2A	175.89 (5)	H9A1—N9A—H9A2	120.0
O1A—Cr1A—O2A	92.18 (5)	C5A—N10A—H10A	120.0
C1A—O1A—Cr1A	133.54 (11)	C5A—N10A—H10B	120.0
C1A—N1A—H1A1	120.0	H10A—N10A—H10B	120.0
C1A—N1A—H1A2	120.0	O5A—C5A—N10A	118.60 (17)
H1A1—N1A—H1A2	120.0	O5A—C5A—N9A	122.19 (16)
C1A—N2A—H2A1	120.0	N10A—C5A—N9A	119.21 (16)
C1A—N2A—H2A2	120.0	C6A—O6A—Cr1A	134.00 (11)
H2A1—N2A—H2A2	120.0	C6A—N11A—H11A	120.0
O1A—C1A—N2A	123.02 (16)	C6A—N11A—H11B	120.0
O1A—C1A—N1A	118.16 (16)	H11A—N11A—H11B	120.0
N2A—C1A—N1A	118.82 (16)	C6A—N12A—H12A	120.0
C2A—O2A—Cr1A	134.53 (11)	C6A—N12A—H12B	120.0
C2A—N3A—H3A1	120.0	H12A—N12A—H12B	120.0
C2A—N3A—H3A2	120.0	O6A—C6A—N12A	122.57 (16)
H3A1—N3A—H3A2	120.0	O6A—C6A—N11A	117.47 (16)
C2A—N4A—H4A1	120.0	N12A—C6A—N11A	119.95 (17)
C2A—N4A—H4A2	120.0	O3B—Cr1B—O2B	110.98 (10)
H4A1—N4A—H4A2	120.0	O3B—Cr1B—O1B	110.57 (9)
O2A—C2A—N4A	118.21 (16)	O2B—Cr1B—O1B	110.20 (10)
O2A—C2A—N3A	122.64 (16)	O3B—Cr1B—O7B	108.93 (8)
N4A—C2A—N3A	119.13 (16)	O2B—Cr1B—O7B	106.82 (9)
C3A—O3A—Cr1A	132.68 (11)	O1B—Cr1B—O7B	109.24 (9)
C3A—N5A—H5A1	120.0	O6B—Cr2B—O4B	110.63 (8)
C3A—N5A—H5A2	120.0	O6B—Cr2B—O5B	109.93 (8)
H5A1—N5A—H5A2	120.0	O4B—Cr2B—O5B	110.14 (8)
C3A—N6A—H6A1	120.0	O6B—Cr2B—O7B	110.82 (8)
C3A—N6A—H6A2	120.0	O4B—Cr2B—O7B	109.98 (8)
H6A1—N6A—H6A2	120.0	O5B—Cr2B—O7B	105.21 (8)
O3A—C3A—N6A	122.05 (15)	Cr2B—O7B—Cr1B	130.26 (10)
O3A—C3A—N5A	118.32 (16)	H1O1—O1W—H2O1	104 (2)
N6A—C3A—N5A	119.63 (15)
Cr1A—O1A—C1A—N2A	−12.6 (3)	Cr1A—O5A—C5A—N9A	−33.6 (2)
Cr1A—O1A—C1A—N1A	167.40 (14)	Cr1A—O6A—C6A—N12A	−23.3 (3)
Cr1A—O2A—C2A—N4A	175.80 (14)	Cr1A—O6A—C6A—N11A	157.35 (14)
Cr1A—O2A—C2A—N3A	−2.8 (3)	O6B—Cr2B—O7B—Cr1B	−39.64 (15)
Cr1A—O3A—C3A—N6A	−26.1 (2)	O4B—Cr2B—O7B—Cr1B	83.00 (13)
Cr1A—O3A—C3A—N5A	154.40 (13)	O5B—Cr2B—O7B—Cr1B	−158.42 (12)
Cr1A—O4A—C4A—N8A	150.59 (14)	O3B—Cr1B—O7B—Cr2B	78.99 (14)
Cr1A—O4A—C4A—N7A	−29.9 (3)	O2B—Cr1B—O7B—Cr2B	−161.07 (13)
Cr1A—O5A—C5A—N10A	146.75 (14)	O1B—Cr1B—O7B—Cr2B	−41.89 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O2Bi	0.87	2.42	3.051 (3)	129
N1A—H1A2···Br1Cii	0.87	2.60	3.4031 (18)	155
N2A—H2A1···O6A	0.87	2.20	2.890 (2)	136
N2A—H2A1···O1W	0.87	2.58	3.230 (3)	132
N2A—H2A2···Br1Cii	0.87	2.73	3.5121 (17)	150
N3A—H3A1···O3A	0.87	2.23	2.866 (2)	130
N3A—H3A2···O5Biii	0.87	2.21	2.972 (2)	147
N4A—H4A1···Br1C	0.87	2.55	3.4070 (18)	171
N4A—H4A2···O5Biii	0.87	2.11	2.900 (2)	151
N5A—H5A1···O6Bi	0.87	2.52	3.174 (2)	133
N5A—H5A2···O3Biv	0.87	2.33	3.108 (2)	150
N6A—H6A1···O4A	0.87	2.17	2.914 (2)	143
N6A—H6A2···O1Biv	0.87	2.15	2.920 (2)	147
N7A—H7A1···O2A	0.87	2.12	2.865 (2)	143
N7A—H7A2···O4Bv	0.87	2.24	3.092 (2)	168
N8A—H8A1···O7B	0.87	2.03	2.883 (2)	166
N8A—H8A2···O5Bv	0.87	2.04	2.875 (2)	162
N9A—H9A1···O1A	0.87	2.22	2.954 (2)	141
N9A—H9A2···O6Biv	0.87	2.21	2.997 (2)	150
N10A—H10A···O1B	0.87	2.29	3.028 (2)	142
N10A—H10B···O4Biv	0.87	2.39	3.184 (2)	151
N11A—H11A···O1W	0.87	2.04	2.892 (3)	167
N11A—H11B···Br1Cvi	0.87	2.57	3.4031 (18)	162
N12A—H12A···O5A	0.87	2.27	2.982 (2)	140
N12A—H12A···O2B	0.87	2.54	3.051 (2)	118
N12A—H12B···Br1Cvi	0.87	2.85	3.6242 (18)	149
O1W—H1O1···Br1C	0.85 (1)	2.51 (1)	3.332 (2)	163 (3)
O1W—H2O1···O5Bvii	0.84 (1)	2.57 (2)	3.315 (3)	149 (3)