Crystal structure of 1,4,8,11-tetra-azonia-cyclo-tetra-decane bis-(dichromate) monohydrate from synchrotron data.

The asymmetric unit of the hydrated title salt, (C10H28N4)[Cr2O7]2·H2O [C10H28N4 = H4(cyclam) = 1,4,8,11-tetra-azonia-cyclo-tetra-deca-ne], contains two half-cations (both completed by crystallographic inversion symmetry), two dichromate anions and one water mol-ecule. The two [CrO7]2- anions exhibit a nearly staggered conformation, with bridging angles of 133.37 (11) and 136.28 (12)°. The distortions of the dichromate anions are due to their participation in hydrogen-bonding inter-actions with the water mol-ecule and the cations. Inter-molecular hydrogen bonds involving the cyclam N-H groups and water O-H groups as donor groups, and the O atoms of the dichromate anions as acceptor groups give rise to a three-dimensional network.

Chemical context

Chromium(VI) compounds are highly cytotoxic and potential carcinogens (Cohen et al., 1993 ▸). A number of treatment methods for the removal of such toxic heavy metal ions in water have been described (Kalidhasan et al., 2016 ▸), and 1,4,8,11-tetra­aza­cyclo­tetra­decane (cyclam) is possibly one of the most useful candidates for this purpose since it has a strong ability to act as an effective metal-ion binding mol­ecule. The aza­macrocycle is a strong basic amine to form a dication, (C10H26N4)2+, or a tetra­cation, (C10H28N4)4+, in both of which all of the N—H bonds are generally active in hydrogen-bond formation. These di- or tetra­ammonium cations may also be suitable candidates for the removal of toxic metal ions. Previously, the syntheses and crystal structures of [H2(cyclam)](ClO4)2 (Nave & Truter, 1974 ▸), [H2(cyclam)]Cl2·0.5H2O (Kim et al., 2009 ▸), [H4(cyclam)](NO3)4·2H2O (Harrowfield et al., 1996 ▸), [H2(cyclam)](maleate)2 (Mireille Ninon et al., 2013 ▸), [H4(cyclam)](HSO4)4 (Said et al., 2013 ▸), [H4(cyclam)]Cl4, [H4(cyclam)]Cl4·4H2O, [H4(cyclam)]Br4·4H2O, [H4(cyclam)](ClO4)4·2H2O (Robinson et al., 1989 ▸) and [H4(cyclam)](SO4)2·6H2O (Subramanian & Zaworotko, 1995 ▸) have been reported. The crystal structure of neutral cyclam has also been determined (Robinson et al., 1989 ▸), but a combination of the 1,4,8,11-tetra­azonia­cyclo­tetra­decane cation with the [CrO7]2− anion has not been reported. We give here details of the preparation of the title compound, a new hydrated organic dichromate(VI) salt, [H4(cyclam)][Cr2O7]2·H2O, (I), and its structural characterization by synchrotron single-crystal X-ray diffraction.

Structural commentary

An ellipsoid plot of the mol­ecular components of (I) along with the atom-numbering scheme is shown in Fig. 1 ▸. The asymmetric unit comprises of two half-cations (both completed by crystallographic inversion symmetry), two dichromate anions and one water mol­ecule. Within the centrosymmetric tetra-protonated amine unit, (C10H28N4)4+, the C—C and N—C bond lengths range from 1.491 (3) to 1.520 (3) Å and from 1.489 (3) to 1.524 (3) Å, respectively. The range of N—C—C and C—N—C angles is 109.84 (19) to 116.69 (18)° and 110.15 (18) to 111.5 (2)°, respectively. Bond lengths and angles within the tetra­ammonium cations are comparable to the corresponding values determined for the cyclam ligand in trans-[Cr(nic-O)2(cyclam)]ClO4 (nic-O = O-coordinating nicotinate; Choi, 2009 ▸), cis-[Cr(ONO)2(cyclam)]NO2 (Choi et al., 2004a ▸), [Cr(ox)(cyclam)]ClO4 (ox = oxalate; Choi et al., 2004b ▸), [Cr(acac)(cyclam)](ClO4)2·0.5H2O (acac = acetyl­acetonate; Subhan et al., 2011 ▸), cis-[Cr(NCS)2(cyclam)]NCS (Moon et al., 2013 ▸) or [CrCl2(cyclam)][Cr(ox)(cyclam)](ClO4)2 (Moon & Choi, 2016 ▸).

Figure 1

The structures of the mol­ecular components in (I), drawn with displacement ellipsoids at the 60% probability level. Dashed lines represent hydrogen-bonding inter­actions.

It is of inter­est to compare the conformation of the [CrO7]2− anion with those found in other ionic crystals. In (I), the two [CrO7]2− anions exhibit a nearly staggered conformation whereas an eclipsed conformation is observed for (C3H5N2)(NH4)[Cr2O7] or (C9H14N)2[Cr2O7] (Zhu, 2012 ▸; Trabelsi et al., 2015 ▸). The conformation of dichromate anions appears to show a dependence on the size of the associated counter-cation (Moon et al., 2015 ▸, 2017 ▸). The Cr1A—O1A—Cr2A and Cr1B—O1B—Cr2B bridging angles in the anions in (I) are 133.37 (11) and 136.28 (12)°, respectively, slightly larger than 130.26 (10)° in [Cr(urea)6][Cr2O7]Br·H2O (Moon et al., 2015 ▸). The smaller Cr1A—O1A—Cr2A bridging angle is probably due to the non-involvement of the terminal oxygen atoms of Cr2A in any hydrogen bond. Cr—Ob (Ob = bridging O atom) bonds range from 1.7711 (19) to 1.799 (2) Å while the Cr—Ot bond lengths to the terminal O atoms vary from 1.590 (2) to 1.6417 (19) Å, with a mean terminal Cr—O bond length of 1.615 Å. The Cr—O bond lengths for atoms involved in hydrogen-bonding inter­actions are slightly longer than the other Cr—O bonds. This trend is similar to that observed for comparable anions in the structures of [Cr(urea)6][Cr2O7]Br·H2O (Moon et al., 2015 ▸), [Cr(NCS)2(cyclam)]2[Cr2O7]·H2O (Moon et al., 2017 ▸) or [Cr(ox)(cyclam)]2[Cr2O7]·8H2O (Moon & Choi, 2017 ▸).

Supra­molecular features

Extensive N—H⋯O and O—H⋯O hydrogen-bonding inter­actions occur in the crystal structure (Table 1 ▸). Two O—H⋯O hydrogen bonds link the water mol­ecule to two neighboring [CrO7]2− anions while N—H⋯O hydrogen bonds inter­connect the (C10H28N4)4+ cations with both anions (Figs. 1 ▸ and 2 ▸). An extensive array of these contacts generates a three-dimensional network (Fig. 2 ▸) and, apart from Coulombic inter­actions, these hydrogen-bonding inter­actions help to stabilize the crystal structure.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1C—H1NC⋯O2B i	0.91	2.45	3.091 (3)	128
N1D—H1ND⋯O6A	0.91	2.38	3.140 (3)	142
N1D—H1ND⋯O7A	0.91	2.16	2.942 (3)	143
N1D—H2ND⋯O6B ii	0.91	1.87	2.768 (3)	169
N2C—H3NC⋯O6A iii	0.91	2.62	3.074 (3)	112
N2C—H4NC⋯O7B iv	0.91	2.42	3.047 (3)	126
N2C—H4NC⋯O2A	0.91	2.52	3.200 (3)	132
N2D—H3ND⋯O6B ii	0.91	2.42	3.198 (3)	144
N2D—H4ND⋯O2B ii	0.91	2.65	3.357 (3)	136
O1W—H1O1⋯O5A v	0.84 (1)	2.38 (10)	2.999 (3)	130 (11)
O1W—H2O1⋯O1B	0.84 (1)	2.05 (4)	2.774 (3)	143 (5)

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

Figure 2

The crystal packing in compound (I), viewed perpendicular to the bc plane. Dashed lines represent N—H⋯O (pink) and O—H⋯O (cyan) hydrogen-bonding inter­actions, respectively. H atoms bound to C atoms have been omitted.

Database survey

A search of the Cambridge Structural Database (Version 5.38, Feb 2017 with two updates; Groom et al. 2016 ▸) revealed a total of 24 hits for compounds containing 1,4,8,11-tetra­azonia­cyclo­tetra­decane (C10H28N4)4+ or 4,11-di­aza-1,8-diazo­nia­cyclo­tetra­decane (C10H26N4)2+ cations, but a combination with dichromate anions has not been reported.

Synthesis and crystallization

Cyclam (98%) was purchased from Sigma–Aldrich and used without further purification. All other chemicals were reagent-grade materials, and were used as received. 0.102 g of chromium trioxide (1 mmol, Sigma–Aldrich) was dissolved in 20 ml of water and 0.012 g of cyclam (0.06 mmol, Sigma–Aldrich) was added at room temperature. The mixture was stirred for 30 minutes and the resulting solution was filtered. The neat filtrate was allowed to stand for one week to give block-like yellow crystals of (I) suitable for X-ray structural analysis.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.99 Å and N—H = 0.91 Å, respectively, and with U iso(H) values of 1.2U eq of the parent atoms. The hydrogen atoms of the solvent water mol­ecule were assigned based on a difference-Fourier map, and were refined with distance restraints of 0.84 (2) Å (using DFIX and DANG commands), and with U iso(H) values of 1.5U eq of the parent atom. The remaining maximum and minimum electron densities in the final Fourier map are located 0.85 and 0.54 Å, respectively, from the Cr1B site. Six reflections with a poor agreement between measured and calculated intensities were omitted from the final refinement cycles.

Table 2

Experimental details

Crystal data
Chemical formula	(C10H28N4)[Cr2O7]2·H2O
M r	654.38
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	200
a, b, c (Å)	10.428 (2), 13.961 (2), 15.490 (2)
β (°)	94.671 (3)
V (Å3)	2247.6 (6)
Z	4
Radiation type	Synchrotron, λ = 0.610 Å
μ (mm−1)	1.28
Crystal size (mm)	0.11 × 0.10 × 0.09
Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 ▸)
T min, T max	0.942, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12953, 6614, 5804
R int	0.016
(sin θ/λ)max (Å−1)	0.706
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.124, 1.09
No. of reflections	6614
No. of parameters	307
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	2.21, −1.04

Computer programs: PAL BL2D-SMDC (Shin et al., 2016 ▸), HKL3000sm (Otwinowski & Minor, 1997 ▸), SHELXT2015 (Sheldrick, 2015a ▸), SHELXL2015 (Sheldrick, 2015b ▸), DIAMOND (Putz & Brandenburg, 2014 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017005771/wm5385sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017005771/wm5385Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017005771/wm5385Isup3.cml

CCDC reference: 1534082

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

(C10H28N4)[Cr2O7]2·H2O	F(000) = 1336
Mr = 654.38	Dx = 1.934 Mg m−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.610 Å
a = 10.428 (2) Å	Cell parameters from 70448 reflections
b = 13.961 (2) Å	θ = 0.4–33.7°
c = 15.490 (2) Å	µ = 1.28 mm−1
β = 94.671 (3)°	T = 200 K
V = 2247.6 (6) Å3	Block, yellow
Z = 4	0.11 × 0.10 × 0.09 mm

ADSC Q210 CCD area detector diffractometer	5804 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.016
ω scan	θmax = 25.5°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.942, Tmax = 1.000	k = −19→19
12953 measured reflections	l = −21→21
6614 independent reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.0712P)2 + 4.2149P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 2.21 e Å−3
6614 reflections	Δρmin = −1.04 e Å−3
307 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.0096 (10)

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.

	x	y	z	Uiso*/Ueq
Cr1A	0.94583 (4)	0.25171 (3)	0.36481 (2)	0.00893 (10)
Cr2A	0.97052 (4)	0.12932 (3)	0.18519 (2)	0.01054 (10)
O1A	0.94853 (19)	0.23337 (12)	0.25072 (11)	0.0152 (3)
O2A	0.9464 (2)	0.16272 (14)	0.08541 (12)	0.0215 (4)
O3A	0.8720 (2)	0.04430 (14)	0.20636 (13)	0.0198 (4)
O4A	1.1160 (2)	0.09255 (16)	0.20477 (14)	0.0239 (4)
O5A	1.05842 (18)	0.18684 (14)	0.41408 (13)	0.0198 (4)
O6A	0.80867 (18)	0.22499 (15)	0.39940 (13)	0.0207 (4)
O7A	0.9714 (2)	0.36520 (13)	0.37925 (12)	0.0189 (4)
Cr1B	0.49741 (4)	0.58036 (3)	0.18882 (2)	0.01299 (10)
Cr2B	0.45749 (4)	0.72591 (3)	0.35345 (2)	0.01274 (10)
O1B	0.5392 (2)	0.66545 (16)	0.27369 (13)	0.0226 (4)
O2B	0.3859 (2)	0.51137 (17)	0.21811 (15)	0.0283 (5)
O3B	0.6245 (2)	0.51689 (16)	0.17659 (13)	0.0244 (4)
O4B	0.4512 (2)	0.63565 (15)	0.09915 (13)	0.0225 (4)
O5B	0.5562 (3)	0.8034 (2)	0.39672 (19)	0.0485 (8)
O6B	0.4180 (2)	0.65172 (15)	0.42912 (13)	0.0222 (4)
O7B	0.3338 (3)	0.7803 (2)	0.31136 (17)	0.0442 (7)
N1C	1.1608 (2)	0.48518 (17)	0.07746 (16)	0.0207 (4)
H1NC	1.192696	0.527486	0.118455	0.025*
H2NC	1.084404	0.508441	0.053719	0.025*
N2C	0.8491 (2)	0.38005 (16)	0.07391 (15)	0.0179 (4)
H3NC	0.905802	0.373982	0.032598	0.021*
H4NC	0.829751	0.320363	0.092561	0.021*
C1C	1.2545 (2)	0.47649 (17)	0.00725 (15)	0.0133 (4)
H1C1	1.338852	0.453735	0.033274	0.016*
H1C2	1.221515	0.428903	−0.036475	0.016*
C2C	1.1387 (2)	0.38925 (17)	0.11984 (15)	0.0129 (4)
H2C1	1.110865	0.341470	0.074936	0.016*
H2C2	1.219961	0.366488	0.150578	0.016*
C3C	1.0374 (2)	0.39918 (15)	0.18280 (12)	0.0071 (3)
H3C1	1.022978	0.335164	0.207745	0.008*
H3C2	1.072279	0.440867	0.230818	0.008*
C4C	0.9100 (2)	0.43839 (17)	0.14937 (15)	0.0125 (4)
H4C1	0.920930	0.505402	0.130394	0.015*
H4C2	0.851635	0.438789	0.196698	0.015*
C5C	0.72907 (19)	0.42821 (15)	0.03596 (13)	0.0068 (3)
H5C1	0.671037	0.437307	0.082792	0.008*
H5C2	0.685296	0.384273	−0.007113	0.008*
N1D	0.74042 (19)	0.43291 (15)	0.45783 (13)	0.0124 (4)
H1ND	0.797863	0.387321	0.444322	0.015*
H2ND	0.694753	0.408892	0.500537	0.015*
N2D	0.6336 (2)	0.57400 (17)	0.58080 (16)	0.0213 (5)
H3ND	0.589300	0.521117	0.561168	0.026*
H4ND	0.676852	0.559214	0.632478	0.026*
C1D	0.5652 (2)	0.36748 (17)	0.35112 (15)	0.0139 (4)
H1D1	0.527317	0.380206	0.291539	0.017*
H1D2	0.619964	0.309743	0.348804	0.017*
C2D	0.6505 (2)	0.45172 (18)	0.38007 (15)	0.0131 (4)
H2D1	0.701386	0.470585	0.331598	0.016*
H2D2	0.594811	0.506624	0.392587	0.016*
C3D	0.8139 (2)	0.52031 (18)	0.49225 (16)	0.0144 (4)
H3D1	0.870329	0.542564	0.447912	0.017*
H3D2	0.869859	0.501556	0.544205	0.017*
C4D	0.7290 (2)	0.60301 (18)	0.51601 (16)	0.0142 (4)
H4D1	0.680965	0.627588	0.462816	0.017*
H4D2	0.783948	0.655524	0.541016	0.017*
C5D	0.5418 (2)	0.65411 (15)	0.59291 (14)	0.0084 (4)
H5D1	0.503368	0.674117	0.535164	0.010*
H5D2	0.591171	0.709254	0.618333	0.010*
O1W	0.7376 (2)	0.75592 (18)	0.19670 (18)	0.0313 (5)
H1O1	0.749 (13)	0.723 (5)	0.152 (4)	0.30 (8)*
H2O1	0.708 (5)	0.718 (3)	0.232 (3)	0.066 (17)*

	U11	U22	U33	U12	U13	U23
Cr1A	0.01239 (17)	0.00745 (17)	0.00736 (17)	0.00232 (12)	0.00323 (12)	0.00134 (12)
Cr2A	0.01754 (19)	0.00764 (17)	0.00646 (17)	0.00091 (13)	0.00113 (12)	−0.00038 (12)
O1A	0.0271 (9)	0.0096 (7)	0.0094 (7)	0.0002 (7)	0.0048 (6)	−0.0016 (6)
O2A	0.0375 (11)	0.0171 (9)	0.0098 (8)	0.0022 (8)	0.0012 (7)	0.0016 (7)
O3A	0.0267 (10)	0.0128 (8)	0.0197 (9)	−0.0043 (7)	−0.0002 (7)	0.0030 (7)
O4A	0.0219 (9)	0.0260 (10)	0.0238 (10)	0.0072 (8)	0.0012 (8)	−0.0015 (8)
O5A	0.0186 (9)	0.0214 (9)	0.0194 (9)	0.0085 (7)	0.0013 (7)	0.0053 (7)
O6A	0.0161 (8)	0.0260 (10)	0.0209 (9)	0.0013 (7)	0.0059 (7)	0.0078 (8)
O7A	0.0306 (10)	0.0104 (8)	0.0159 (8)	0.0000 (7)	0.0036 (7)	−0.0028 (6)
Cr1B	0.01447 (19)	0.01425 (19)	0.01028 (18)	0.00271 (13)	0.00115 (13)	−0.00104 (13)
Cr2B	0.0189 (2)	0.01113 (18)	0.00895 (17)	0.00155 (13)	0.00592 (13)	0.00160 (13)
O1B	0.0241 (9)	0.0264 (10)	0.0181 (9)	−0.0004 (8)	0.0067 (7)	−0.0098 (8)
O2B	0.0254 (10)	0.0306 (11)	0.0292 (11)	−0.0093 (9)	0.0038 (8)	0.0042 (9)
O3B	0.0250 (10)	0.0290 (11)	0.0194 (9)	0.0134 (8)	0.0023 (7)	−0.0046 (8)
O4B	0.0276 (10)	0.0218 (10)	0.0171 (9)	0.0010 (8)	−0.0051 (7)	0.0036 (7)
O5B	0.0656 (19)	0.0379 (14)	0.0446 (15)	−0.0317 (14)	0.0206 (14)	−0.0224 (12)
O6B	0.0291 (10)	0.0231 (10)	0.0149 (8)	−0.0037 (8)	0.0040 (7)	0.0079 (7)
O7B	0.0396 (14)	0.0612 (18)	0.0347 (13)	0.0314 (13)	0.0199 (11)	0.0275 (13)
N1C	0.0239 (11)	0.0177 (10)	0.0207 (10)	0.0008 (9)	0.0035 (8)	0.0042 (9)
N2C	0.0230 (11)	0.0143 (10)	0.0165 (10)	−0.0009 (8)	0.0028 (8)	−0.0007 (8)
C1C	0.0150 (10)	0.0110 (10)	0.0140 (10)	0.0001 (8)	0.0020 (8)	0.0013 (8)
C2C	0.0151 (10)	0.0113 (10)	0.0125 (9)	0.0006 (8)	0.0011 (8)	0.0028 (8)
C3C	0.0131 (9)	0.0052 (8)	0.0028 (8)	−0.0017 (7)	0.0005 (7)	0.0022 (6)
C4C	0.0161 (10)	0.0119 (10)	0.0098 (9)	0.0001 (8)	0.0019 (8)	−0.0017 (8)
C5C	0.0083 (8)	0.0076 (8)	0.0046 (8)	−0.0029 (7)	0.0020 (6)	0.0005 (7)
N1D	0.0140 (9)	0.0138 (9)	0.0096 (8)	0.0049 (7)	0.0021 (7)	0.0015 (7)
N2D	0.0226 (11)	0.0189 (11)	0.0228 (11)	0.0038 (9)	0.0039 (9)	0.0000 (9)
C1D	0.0164 (10)	0.0149 (10)	0.0106 (10)	0.0037 (8)	0.0017 (8)	−0.0030 (8)
C2D	0.0136 (10)	0.0159 (10)	0.0098 (9)	0.0021 (8)	0.0000 (7)	0.0024 (8)
C3D	0.0108 (9)	0.0183 (11)	0.0141 (10)	0.0000 (8)	0.0021 (8)	0.0024 (9)
C4D	0.0148 (10)	0.0128 (10)	0.0152 (10)	−0.0017 (8)	0.0019 (8)	−0.0002 (8)
C5D	0.0107 (9)	0.0054 (8)	0.0093 (9)	0.0017 (7)	0.0018 (7)	−0.0019 (7)
O1W	0.0229 (10)	0.0311 (12)	0.0405 (13)	0.0049 (9)	0.0053 (9)	0.0165 (10)

Cr1A—O6A	1.6114 (19)	C3C—C4C	1.491 (3)
Cr1A—O7A	1.6192 (19)	C3C—H3C1	0.9900
Cr1A—O5A	1.6233 (19)	C3C—H3C2	0.9900
Cr1A—O1A	1.7882 (18)	C4C—H4C1	0.9900
Cr2A—O4A	1.607 (2)	C4C—H4C2	0.9900
Cr2A—O2A	1.6143 (19)	C5C—H5C1	0.9900
Cr2A—O3A	1.6209 (19)	C5C—H5C2	0.9900
Cr2A—O1A	1.7975 (18)	N1D—C2D	1.489 (3)
Cr1B—O2B	1.603 (2)	N1D—C3D	1.515 (3)
Cr1B—O3B	1.618 (2)	N1D—H1ND	0.9100
Cr1B—O4B	1.627 (2)	N1D—H2ND	0.9100
Cr1B—O1B	1.799 (2)	N2D—C5D	1.494 (3)
Cr2B—O7B	1.590 (2)	N2D—C4D	1.524 (3)
Cr2B—O5B	1.602 (3)	N2D—H3ND	0.9100
Cr2B—O6B	1.6417 (19)	N2D—H4ND	0.9100
Cr2B—O1B	1.7711 (19)	C1D—C5Dii	1.498 (3)
N1C—C2C	1.517 (3)	C1D—C2D	1.520 (3)
N1C—C1C	1.524 (3)	C1D—H1D1	0.9900
N1C—H1NC	0.9100	C1D—H1D2	0.9900
N1C—H2NC	0.9100	C2D—H2D1	0.9900
N2C—C5C	1.498 (3)	C2D—H2D2	0.9900
N2C—C4C	1.521 (3)	C3D—C4D	1.519 (3)
N2C—H3NC	0.9100	C3D—H3D1	0.9900
N2C—H4NC	0.9100	C3D—H3D2	0.9900
C1C—C5Ci	1.506 (3)	C4D—H4D1	0.9900
C1C—H1C1	0.9900	C4D—H4D2	0.9900
C1C—H1C2	0.9900	C5D—H5D1	0.9900
C2C—C3C	1.501 (3)	C5D—H5D2	0.9900
C2C—H2C1	0.9900	O1W—H1O1	0.844 (10)
C2C—H2C2	0.9900	O1W—H2O1	0.844 (10)
O6A—Cr1A—O7A	108.74 (11)	C3C—C4C—N2C	112.02 (19)
O6A—Cr1A—O5A	110.00 (10)	C3C—C4C—H4C1	109.2
O7A—Cr1A—O5A	112.10 (11)	N2C—C4C—H4C1	109.2
O6A—Cr1A—O1A	112.41 (10)	C3C—C4C—H4C2	109.2
O7A—Cr1A—O1A	105.13 (9)	N2C—C4C—H4C2	109.2
O5A—Cr1A—O1A	108.41 (9)	H4C1—C4C—H4C2	107.9
O4A—Cr2A—O2A	110.11 (11)	N2C—C5C—C1Ci	116.69 (18)
O4A—Cr2A—O3A	109.41 (11)	N2C—C5C—H5C1	108.1
O2A—Cr2A—O3A	110.70 (11)	C1Ci—C5C—H5C1	108.1
O4A—Cr2A—O1A	108.27 (10)	N2C—C5C—H5C2	108.1
O2A—Cr2A—O1A	106.87 (9)	C1Ci—C5C—H5C2	108.1
O3A—Cr2A—O1A	111.43 (10)	H5C1—C5C—H5C2	107.3
Cr1A—O1A—Cr2A	133.37 (11)	C2D—N1D—C3D	114.21 (19)
O2B—Cr1B—O3B	108.89 (13)	C2D—N1D—H1ND	108.7
O2B—Cr1B—O4B	110.81 (11)	C3D—N1D—H1ND	108.7
O3B—Cr1B—O4B	110.38 (11)	C2D—N1D—H2ND	108.7
O2B—Cr1B—O1B	109.15 (11)	C3D—N1D—H2ND	108.7
O3B—Cr1B—O1B	107.16 (10)	H1ND—N1D—H2ND	107.6
O4B—Cr1B—O1B	110.35 (11)	C5D—N2D—C4D	110.1 (2)
O7B—Cr2B—O5B	108.74 (19)	C5D—N2D—H3ND	109.6
O7B—Cr2B—O6B	110.59 (12)	C4D—N2D—H3ND	109.6
O5B—Cr2B—O6B	108.50 (14)	C5D—N2D—H4ND	109.6
O7B—Cr2B—O1B	111.22 (12)	C4D—N2D—H4ND	109.6
O5B—Cr2B—O1B	106.51 (13)	H3ND—N2D—H4ND	108.2
O6B—Cr2B—O1B	111.12 (11)	C5Dii—C1D—C2D	115.47 (19)
Cr2B—O1B—Cr1B	136.28 (12)	C5Dii—C1D—H1D1	108.4
C2C—N1C—C1C	111.5 (2)	C2D—C1D—H1D1	108.4
C2C—N1C—H1NC	109.3	C5Dii—C1D—H1D2	108.4
C1C—N1C—H1NC	109.3	C2D—C1D—H1D2	108.4
C2C—N1C—H2NC	109.3	H1D1—C1D—H1D2	107.5
C1C—N1C—H2NC	109.3	N1D—C2D—C1D	114.7 (2)
H1NC—N1C—H2NC	108.0	N1D—C2D—H2D1	108.6
C5C—N2C—C4C	110.15 (18)	C1D—C2D—H2D1	108.6
C5C—N2C—H3NC	109.6	N1D—C2D—H2D2	108.6
C4C—N2C—H3NC	109.6	C1D—C2D—H2D2	108.6
C5C—N2C—H4NC	109.6	H2D1—C2D—H2D2	107.6
C4C—N2C—H4NC	109.6	N1D—C3D—C4D	114.17 (19)
H3NC—N2C—H4NC	108.1	N1D—C3D—H3D1	108.7
C5Ci—C1C—N1C	110.47 (19)	C4D—C3D—H3D1	108.7
C5Ci—C1C—H1C1	109.6	N1D—C3D—H3D2	108.7
N1C—C1C—H1C1	109.6	C4D—C3D—H3D2	108.7
C5Ci—C1C—H1C2	109.6	H3D1—C3D—H3D2	107.6
N1C—C1C—H1C2	109.6	C3D—C4D—N2D	112.5 (2)
H1C1—C1C—H1C2	108.1	C3D—C4D—H4D1	109.1
C3C—C2C—N1C	109.84 (19)	N2D—C4D—H4D1	109.1
C3C—C2C—H2C1	109.7	C3D—C4D—H4D2	109.1
N1C—C2C—H2C1	109.7	N2D—C4D—H4D2	109.1
C3C—C2C—H2C2	109.7	H4D1—C4D—H4D2	107.8
N1C—C2C—H2C2	109.7	N2D—C5D—C1Dii	115.92 (19)
H2C1—C2C—H2C2	108.2	N2D—C5D—H5D1	108.3
C4C—C3C—C2C	117.56 (18)	C1Dii—C5D—H5D1	108.3
C4C—C3C—H3C1	107.9	N2D—C5D—H5D2	108.3
C2C—C3C—H3C1	107.9	C1Dii—C5D—H5D2	108.3
C4C—C3C—H3C2	107.9	H5D1—C5D—H5D2	107.4
C2C—C3C—H3C2	107.9	H1O1—O1W—H2O1	106 (3)
H3C1—C3C—H3C2	107.2
O6A—Cr1A—O1A—Cr2A	−81.13 (17)	C2C—N1C—C1C—C5Ci	177.91 (19)
O7A—Cr1A—O1A—Cr2A	160.74 (15)	C1C—N1C—C2C—C3C	−175.00 (19)
O5A—Cr1A—O1A—Cr2A	40.70 (18)	N1C—C2C—C3C—C4C	55.8 (3)
O4A—Cr2A—O1A—Cr1A	−67.38 (18)	C2C—C3C—C4C—N2C	56.8 (3)
O2A—Cr2A—O1A—Cr1A	174.04 (15)	C5C—N2C—C4C—C3C	−173.51 (18)
O3A—Cr2A—O1A—Cr1A	52.99 (18)	C4C—N2C—C5C—C1Ci	65.9 (2)
O7B—Cr2B—O1B—Cr1B	−53.2 (2)	C3D—N1D—C2D—C1D	−173.36 (19)
O5B—Cr2B—O1B—Cr1B	−171.5 (2)	C5Dii—C1D—C2D—N1D	73.5 (3)
O6B—Cr2B—O1B—Cr1B	70.5 (2)	C2D—N1D—C3D—C4D	57.5 (3)
O2B—Cr1B—O1B—Cr2B	−32.7 (2)	N1D—C3D—C4D—N2D	55.5 (3)
O3B—Cr1B—O1B—Cr2B	−150.48 (18)	C5D—N2D—C4D—C3D	−172.66 (19)
O4B—Cr1B—O1B—Cr2B	89.3 (2)	C4D—N2D—C5D—C1Dii	174.65 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1C—H1NC···O2Biii	0.91	2.45	3.091 (3)	128
N1D—H1ND···O6A	0.91	2.38	3.140 (3)	142
N1D—H1ND···O7A	0.91	2.16	2.942 (3)	143
N1D—H2ND···O6Bii	0.91	1.87	2.768 (3)	169
N2C—H3NC···O6Aiv	0.91	2.62	3.074 (3)	112
N2C—H4NC···O7Bv	0.91	2.42	3.047 (3)	126
N2C—H4NC···O2A	0.91	2.52	3.200 (3)	132
N2D—H3ND···O6Bii	0.91	2.42	3.198 (3)	144
N2D—H4ND···O2Bii	0.91	2.65	3.357 (3)	136
O1W—H1O1···O5Avi	0.84 (1)	2.38 (10)	2.999 (3)	130 (11)
O1W—H2O1···O1B	0.84 (1)	2.05 (4)	2.774 (3)	143 (5)