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Acta Cryst. (2007). E63, m3069-m3070    [ doi:10.1107/S1600536807056176 ]

(Acetylacetonato)aqua(2,2',2''-terpyridine)chromium(III) bis(perchlorate) dihydrate hexamethylphosphoramide solvate

N. Cloete and H. G. Visser

Abstract top

The title compound, [Cr(C5H8O2)(C15H11N3)(H2O)](ClO4)2·2H2O·C6H18N3OP, adopts a distorted octahedral configuration about the CrIII atom, mainly due to the rigidity of the terpyridyl ligand. The N-Cr-N bite angles are significantly distorted from 90° at 78.3 (1) and 78.6 (1)°. The Cr-N bond distances vary between 1.998 (1) and 2.068 (1) Å. The crystal packing is controlled by hydrogen bonding and [pi]-stacking, with an interplanar separation of 3.263 (2) Å.

Comment top

The title compound, [Cr(acac)(H2O)(terpy)]·2(ClO4)·2(H2O)·(PON3C6H18), (terpy = 2,2',2''-terpyridine and acac = acetyl acetonoate), (I), contains a chromium(III) atom which is octahedrally surrounded by three N atoms (N1, N2 and N3) of the terpy ligand, two O atoms from the acac ligand and another O atom from the coordinated H2O molecule (Figure 1). The Cr-atom in (I) adopts a distorted octahedral geometry where the mean intraligand N—Cr—N bond angle is 78.4 (1)°, similar to bond angles in mer-[CrCl3(terpy)] (Cloete et al., 2007). The rigidity of the terpyridyl group necessatates the above mentioned bite angles to be much smaller than 90°. The O1—Cr—O2 bond angle is 91.1 (1)° which is equal to the average intramolecular O—Cr—O bond angle reported in [Cr(acac)3 (Morosin, 1965)].

The mean Cr—N(peripheral) distance of 2.062 (1) Å is slightly longer than the Cr—N(central) bond distance (1.998 (1) Å). This difference of approximately 0.08 Å has also been observed in mer-[Cr(terpy)2]3+ (Wickramasinghe et al., 1982) and in the metallo-mono(terpy) complexes mer-[CrCl3(terpy)] (Cloete et al., 2007), [mer-[GaCl2(terpy)] (0.078 Å) (Beran et al., 1970), mer-[ZnCl2(terpy)] (0.12 Å) (Einstein et al., 1966) and mer-[(CH3)2SnCl(terpy)]+ (0.08 Å) (Einstein et al., 1968). The C—C bond distances for the acac ligand range between 1.384 (2) and 1.496 Å. These bond lengths are consistent with the partial double bond character of the acetylacetonate ligand in which the electrons are delocalized in the chelate ring.

The other bonds in complex (I) fall within the same range as the corresponding complexes (Beran et al., 1970; Cloete et al., 2007; Einstein et al., 1966; Einstein et al., 1968; Liu & Verkade, 1998; Shiren & Tanaka, 2002 and Visser et al., 2005).

The [Cr(acac)(H2O)(terpy)] cations are packed diagonally across the ac plane with the perchlorate anions, hexamethylphosphoramide and water molecules filling the spaces in between (Fig. 2). The molecules within the structure are linked by an extensive network of intermolecular hydrogen bonds and non-conventinal H-bonds of the types C—H···O and C—H···N. The crystal packing also seems to be influenced by π-π stacking interactions between the terpy moieties (Fig. 2) with an interplanar separation of 3.263 (2) Å.

Related literature top

For similar complexes, see: Beran et al. (1970); Cloete et al. (2007); Einstein & Penfold (1966, 1968); Liu & Verkade (1998); Morosin (1965); Shiren & Tanaka (2002); Visser et al. (2005); Wickramasinghe et al. (1982). For the synthesis of the starting complex mer-[CrCl3(terpy)], see: Cloete et al. (2007).

Experimental top

[Cr(terpy)Cl3] (Cloete et al., 2007) (1.5 g, 3.2 mmole) was dissolved in methanol (300 ml). AgClO4 (0.662 g, 3.2 mmole) was added to the methanol solution and stirred at room temperature for 12 h. The solution was filtered. NaOH (0.13 g, 3.2 mmole) and acetylacetone (3.3 ml 3.2 mmole) was added to the filtrate. Reaction mixture was stirred for another 12 h after which the solution was acidified with HClO4 (5 ml, 60% v/v) and stirred for two hours. H2O (100 ml) was added and the solution was left to slowly evaporate at room temperature. Single red cystals were obtained after 1 day which were suitable for X-ray crystallography. Yield: 0.199 g (76.1%)

Refinement top

The aromatic, methylene and methyl (hexamethylphosphoramide molecule) hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) and 1.2Ueq(C), respectively. The hydrogen atoms on the methyl groups of the acac ligand were constrained to ride on their parent atoms and idealized as rotating CH3 groups. Aqua H atoms were located in a difference Fourier map and then refined isotropically. The H atom on the C3 atom of the acac group was located in a difference Fourier map and then refined isotropically. The maximum and the minimum residual electron density are located 0.69 Å from N6 and 0.69 Å from Cr1, respectively, indicating no physical meaning.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. : View of (I) with 50% probability displacement ellipsoids; H-atoms were omitted for clarity.
[Figure 2] Fig. 2. : View of (I) along the b axis, illustrating selected H-bonds and π stacking. i) (−x, 2 − y, −z) ii) (x, y, −1 + z) iii) (3/2 − x, 1/2 + y, 1/2 − z)
(Acetylacetonato)aqua(2,2',2''-terpyridine)chromium(III) bis(perchlorate) dihydrate hexamethylphosphoramide solvate top
Crystal data top
[Cr(C5H7O2)(C15H11N3)(H2O1)](ClO4)2·2(H2O)·C6H18N3OPF000 = 1700
Mr = 816.53Dx = 1.537 Mg m−3
Dm = 1.54 Mg m−3
Dm measured by not measured
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9416 reflections
a = 13.2524 (4) Åθ = 2.5–28.3º
b = 13.5607 (4) ŵ = 0.59 mm−1
c = 19.7271 (6) ÅT = 101 (2) K
β = 95.588 (1)ºCuboid, red
V = 3528.35 (18) Å30.26 × 0.24 × 0.19 mm
Z = 4
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer		7534 reflections with I > 2σ(I)
T = 101(2) KRint = 0.032
ω and φ scansθmax = 28.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		θmin = 1.8º
Tmin = 0.850, Tmax = 0.899h = −17→17
61605 measured reflectionsk = −18→18
8750 independent reflectionsl = −24→26
Refinement top
Refinement on F2H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0529P)2 + 4.3676P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.030(Δ/σ)max = 0.001
wR(F2) = 0.08Δρmax = 0.4 e Å−3
S = 1.02Δρmin = −0.42 e Å−3
8750 reflectionsExtinction correction: none
477 parameters
Crystal data top
[Cr(C5H7O2)(C15H11N3)(H2O1)](ClO4)2·2(H2O)·C6H18N3OPV = 3528.35 (18) Å3
Mr = 816.53Z = 4
Monoclinic, P21/nMo Kα
a = 13.2524 (4) ŵ = 0.59 mm−1
b = 13.5607 (4) ÅT = 101 (2) K
c = 19.7271 (6) Å0.26 × 0.24 × 0.19 mm
β = 95.588 (1)º
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer		8750 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		7534 reflections with I > 2σ(I)
Tmin = 0.850, Tmax = 0.899Rint = 0.032
61605 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030477 parameters
wR(F2) = 0.08H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.4 e Å−3
8750 reflectionsΔρmin = −0.42 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.126363 (16)0.768594 (16)0.120659 (11)0.01100 (6)
Cl10.19255 (3)0.33434 (3)0.091107 (18)0.01726 (8)
Cl20.69017 (3)0.49729 (3)0.254242 (19)0.02045 (9)
O1−0.02022 (8)0.76518 (7)0.11518 (5)0.0145 (2)
O20.13586 (8)0.67037 (8)0.19157 (5)0.0160 (2)
N20.12138 (9)0.87546 (9)0.05072 (6)0.0127 (2)
N30.12156 (9)0.68837 (9)0.03127 (6)0.0137 (2)
N10.12924 (9)0.89261 (9)0.18065 (6)0.0141 (2)
O60.24232 (9)0.25598 (9)0.13100 (6)0.0260 (3)
P10.43832 (3)0.77800 (3)0.995845 (19)0.01538 (8)
O120.34383 (8)0.82187 (9)1.01873 (6)0.0222 (2)
N40.42298 (10)0.75554 (10)0.91434 (7)0.0199 (3)
N50.47021 (10)0.66964 (10)1.02906 (7)0.0203 (3)
O130.39785 (10)0.80887 (10)0.23635 (7)0.0252 (3)
O140.89534 (10)0.29744 (12)0.25721 (7)0.0289 (3)
N60.53124 (10)0.85556 (10)1.01509 (7)0.0206 (3)
C70.35895 (13)0.81940 (15)0.86919 (9)0.0281 (4)
H7A0.31910.86080.89570.042*
H7B0.31480.77980.83880.042*
H7C0.40070.85970.84330.042*
C80.39334 (13)0.59136 (13)1.02112 (10)0.0288 (4)
H8A0.35110.6010.97930.043*
H8B0.35240.59351.05870.043*
H8C0.42620.52841.02020.043*
C90.53796 (14)0.66036 (14)1.09146 (9)0.0299 (4)
H9A0.58650.71311.09390.045*
H9B0.57280.59831.09150.045*
H9C0.49920.66351.13010.045*
C170.53491 (16)0.91838 (14)1.07527 (9)0.0324 (4)
H17A0.47080.91581.09410.049*
H17B0.54890.98511.06280.049*
H17C0.58740.89561.10860.049*
C60.48678 (14)0.68963 (14)0.87875 (9)0.0298 (4)
H6A0.52690.64970.91130.045*
H6B0.53070.72780.8530.045*
H6C0.44480.64790.84850.045*
C100.62493 (13)0.85386 (15)0.98238 (10)0.0298 (4)
H10A0.61690.81140.94330.045*
H10B0.6790.82971.01390.045*
H10C0.64070.91940.96830.045*
O30.27545 (8)0.76660 (8)0.12612 (6)0.0162 (2)
H5A0.3840 (19)0.8279 (19)0.2696 (14)0.047 (8)*
H5B0.465 (2)0.8070 (18)0.2371 (12)0.045 (7)*
H4B0.8704 (19)0.244 (2)0.2575 (13)0.045 (7)*
H4A0.852 (2)0.342 (2)0.2664 (16)0.078 (10)*
H450.3038 (17)0.7814 (16)0.1576 (12)0.030 (6)*
H460.3014 (19)0.7886 (18)0.0903 (14)0.050 (7)*
C310.11945 (11)0.74333 (11)−0.02662 (7)0.0144 (3)
O40.11986 (9)0.29300 (9)0.04007 (6)0.0284 (3)
O50.26586 (9)0.39128 (9)0.05905 (6)0.0263 (3)
C250.12033 (10)0.85093 (11)−0.01524 (7)0.0145 (3)
C220.12551 (11)1.04583 (11)0.02463 (8)0.0182 (3)
H220.1281.11130.03870.022*
C340.11710 (12)0.54218 (12)−0.03595 (8)0.0214 (3)
H340.11580.4737−0.03820.026*
C130.12692 (13)1.06842 (12)0.25091 (9)0.0252 (4)
H130.12561.12760.27470.03*
O70.14090 (9)0.39758 (9)0.13592 (6)0.0250 (3)
C150.12453 (11)0.97999 (11)0.14630 (8)0.0154 (3)
C240.12035 (11)0.92365 (12)−0.06455 (8)0.0177 (3)
H240.11840.9073−0.11040.021*
C140.12233 (12)1.06858 (11)0.18027 (9)0.0212 (3)
H140.11781.12770.15630.025*
C120.13348 (13)0.98032 (12)0.28550 (9)0.0233 (3)
H120.13750.97910.33280.028*
C20.06322 (11)0.62566 (11)0.21764 (7)0.0153 (3)
C4−0.07570 (11)0.70747 (11)0.14682 (7)0.0148 (3)
C3−0.03864 (11)0.63886 (11)0.19608 (8)0.0175 (3)
H3−0.08540.59950.21570.021*
C210.12382 (10)0.96977 (11)0.07163 (8)0.0146 (3)
C5−0.18745 (12)0.71765 (12)0.12873 (8)0.0213 (3)
H5C−0.20250.71090.08040.032*
H5D−0.20930.78130.14280.032*
H5E−0.22230.66720.15140.032*
C320.11698 (11)0.69970 (12)−0.08987 (8)0.0193 (3)
H320.11610.7382−0.12890.023*
C330.11581 (12)0.59778 (13)−0.09459 (8)0.0228 (3)
H330.11420.5671−0.13690.027*
O80.67088 (11)0.59924 (9)0.26969 (7)0.0355 (3)
C350.12030 (11)0.58980 (11)0.02628 (8)0.0173 (3)
H350.12160.55230.06580.021*
C110.13407 (11)0.89343 (12)0.24870 (8)0.0183 (3)
H110.1380.83370.2720.022*
O90.69011 (12)0.48494 (11)0.18257 (7)0.0400 (3)
O110.61525 (11)0.43677 (10)0.28030 (7)0.0383 (3)
O100.78831 (11)0.47091 (11)0.28708 (9)0.0482 (4)
C230.12333 (11)1.02168 (12)−0.04377 (8)0.0196 (3)
H230.12391.0716−0.07610.024*
C10.09592 (13)0.55771 (12)0.27532 (8)0.0232 (3)
H1A0.14170.50930.26040.035*
H1B0.03760.52530.29030.035*
H1C0.12940.59490.31230.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.01239 (11)0.00971 (11)0.01106 (11)0.00019 (8)0.00199 (8)0.00174 (8)
Cl10.01874 (17)0.01400 (16)0.01917 (18)−0.00186 (13)0.00244 (13)0.00061 (13)
Cl20.02155 (18)0.01963 (18)0.01980 (18)−0.00030 (14)0.00005 (14)0.00105 (14)
O10.0145 (5)0.0144 (5)0.0149 (5)−0.0007 (4)0.0027 (4)0.0021 (4)
O20.0179 (5)0.0144 (5)0.0159 (5)0.0002 (4)0.0023 (4)0.0037 (4)
N20.0106 (5)0.0127 (6)0.0150 (6)0.0003 (4)0.0024 (4)0.0027 (5)
N30.0126 (6)0.0140 (6)0.0147 (6)0.0000 (4)0.0017 (4)0.0011 (5)
N10.0134 (6)0.0129 (6)0.0161 (6)0.0004 (4)0.0027 (4)0.0001 (5)
O60.0289 (6)0.0195 (6)0.0300 (6)0.0038 (5)0.0047 (5)0.0084 (5)
P10.01319 (17)0.01865 (19)0.01444 (18)0.00062 (14)0.00207 (13)0.00170 (14)
O120.0190 (5)0.0292 (6)0.0191 (6)0.0052 (5)0.0065 (4)0.0047 (5)
N40.0168 (6)0.0264 (7)0.0165 (6)0.0026 (5)0.0008 (5)−0.0011 (5)
N50.0177 (6)0.0196 (7)0.0229 (7)−0.0013 (5)−0.0013 (5)0.0035 (5)
O130.0238 (7)0.0298 (7)0.0217 (6)−0.0018 (5)0.0006 (5)−0.0059 (5)
O140.0271 (7)0.0302 (7)0.0295 (7)−0.0027 (6)0.0024 (5)−0.0020 (6)
N60.0203 (6)0.0215 (7)0.0199 (6)−0.0036 (5)0.0015 (5)−0.0006 (5)
C70.0242 (8)0.0402 (10)0.0193 (8)0.0053 (7)−0.0006 (6)0.0048 (7)
C80.0249 (9)0.0204 (8)0.0404 (10)−0.0033 (7)0.0002 (7)0.0049 (7)
C90.0309 (9)0.0274 (9)0.0294 (9)0.0016 (7)−0.0074 (7)0.0079 (7)
C170.0436 (11)0.0278 (9)0.0245 (9)−0.0035 (8)−0.0041 (8)−0.0047 (7)
C60.0297 (9)0.0349 (10)0.0249 (9)0.0043 (8)0.0036 (7)−0.0109 (8)
C100.0177 (8)0.0378 (10)0.0339 (10)−0.0062 (7)0.0020 (7)0.0026 (8)
O30.0148 (5)0.0207 (6)0.0132 (5)0.0002 (4)0.0017 (4)0.0014 (4)
C310.0117 (6)0.0169 (7)0.0148 (7)0.0009 (5)0.0020 (5)0.0021 (6)
O40.0258 (6)0.0299 (7)0.0285 (6)−0.0049 (5)−0.0022 (5)−0.0083 (5)
O50.0258 (6)0.0238 (6)0.0302 (6)−0.0049 (5)0.0081 (5)0.0067 (5)
C250.0098 (6)0.0187 (7)0.0153 (7)0.0010 (5)0.0023 (5)0.0034 (6)
C220.0134 (7)0.0134 (7)0.0280 (8)0.0000 (5)0.0027 (6)0.0052 (6)
C340.0225 (8)0.0169 (7)0.0246 (8)0.0004 (6)0.0015 (6)−0.0055 (6)
C130.0270 (8)0.0188 (8)0.0299 (9)−0.0021 (6)0.0033 (7)−0.0099 (7)
O70.0334 (7)0.0190 (6)0.0234 (6)0.0038 (5)0.0071 (5)−0.0017 (5)
C150.0121 (6)0.0135 (7)0.0205 (7)−0.0010 (5)0.0020 (5)0.0002 (6)
C240.0125 (7)0.0246 (8)0.0162 (7)0.0019 (6)0.0026 (5)0.0062 (6)
C140.0215 (8)0.0130 (7)0.0293 (9)−0.0015 (6)0.0041 (6)−0.0013 (6)
C120.0251 (8)0.0254 (8)0.0193 (8)−0.0003 (7)0.0023 (6)−0.0055 (6)
C20.0234 (7)0.0106 (7)0.0126 (7)−0.0005 (5)0.0043 (5)−0.0008 (5)
C40.0174 (7)0.0143 (7)0.0132 (7)−0.0018 (5)0.0037 (5)−0.0031 (5)
C30.0205 (7)0.0155 (7)0.0173 (7)−0.0042 (6)0.0062 (6)0.0021 (6)
C210.0106 (6)0.0127 (7)0.0207 (7)−0.0004 (5)0.0029 (5)0.0026 (6)
C50.0160 (7)0.0246 (8)0.0235 (8)−0.0020 (6)0.0037 (6)0.0015 (6)
C320.0176 (7)0.0258 (8)0.0145 (7)0.0000 (6)0.0014 (5)0.0002 (6)
C330.0219 (8)0.0285 (9)0.0179 (7)0.0001 (7)0.0014 (6)−0.0076 (6)
O80.0512 (8)0.0200 (6)0.0347 (7)0.0055 (6)0.0011 (6)0.0000 (5)
C350.0177 (7)0.0152 (7)0.0189 (7)0.0008 (6)0.0018 (6)0.0010 (6)
C110.0192 (7)0.0190 (7)0.0168 (7)0.0001 (6)0.0022 (6)−0.0007 (6)
O90.0579 (9)0.0408 (8)0.0224 (7)−0.0050 (7)0.0103 (6)−0.0030 (6)
O110.0415 (8)0.0369 (8)0.0384 (8)−0.0133 (6)0.0126 (6)0.0047 (6)
O100.0316 (7)0.0369 (8)0.0707 (11)0.0079 (6)−0.0222 (7)−0.0106 (8)
C230.0146 (7)0.0200 (8)0.0245 (8)0.0001 (6)0.0034 (6)0.0121 (6)
C10.0283 (8)0.0210 (8)0.0208 (8)0.0025 (6)0.0049 (6)0.0086 (6)
Geometric parameters (Å, °) top
Cr1—O21.9268 (10)C17—H17B0.96
Cr1—O11.9356 (10)C17—H17C0.96
Cr1—O31.9684 (11)C6—H6A0.96
Cr1—N21.9976 (12)C6—H6B0.96
Cr1—N12.0547 (12)C6—H6C0.96
Cr1—N32.0676 (12)C10—H10A0.96
Cl1—O51.4352 (12)C10—H10B0.96
Cl1—O41.4376 (12)C10—H10C0.96
Cl1—O61.4430 (12)O3—H450.72 (2)
Cl1—O71.4503 (12)O3—H460.87 (3)
Cl2—O111.4222 (13)C31—C321.379 (2)
Cl2—O91.4236 (14)C31—C251.476 (2)
Cl2—O101.4405 (14)C25—C241.385 (2)
Cl2—O81.4439 (13)C22—C231.386 (2)
O1—C41.2776 (18)C22—C211.389 (2)
O2—C21.2864 (18)C22—H220.93
N2—C251.3418 (19)C34—C331.380 (2)
N2—C211.3431 (19)C34—C351.384 (2)
N3—C351.3403 (19)C34—H340.93
N3—C311.3617 (19)C13—C121.374 (2)
N1—C111.3376 (19)C13—C141.389 (2)
N1—C151.3635 (19)C13—H130.93
P1—O121.4953 (11)C15—C141.377 (2)
P1—N41.6297 (13)C15—C211.479 (2)
P1—N61.6356 (14)C24—C231.391 (2)
P1—N51.6473 (14)C24—H240.93
N4—C71.455 (2)C14—H140.93
N4—C61.457 (2)C12—C111.384 (2)
N5—C91.457 (2)C12—H120.93
N5—C81.469 (2)C2—C31.387 (2)
O13—H5A0.75 (3)C2—C11.495 (2)
O13—H5B0.89 (3)C4—C31.399 (2)
O14—H4B0.80 (3)C4—C51.496 (2)
O14—H4A0.86 (3)C3—H30.93
N6—C101.454 (2)C5—H5C0.96
N6—C171.458 (2)C5—H5D0.96
C7—H7A0.96C5—H5E0.96
C7—H7B0.96C32—C331.385 (2)
C7—H7C0.96C32—H320.93
C8—H8A0.96C33—H330.93
C8—H8B0.96C35—H350.93
C8—H8C0.96C11—H110.93
C9—H9A0.96C23—H230.93
C9—H9B0.96C1—H1A0.96
C9—H9C0.96C1—H1B0.96
C17—H17A0.96C1—H1C0.96
O2—Cr1—O191.05 (4)N4—C6—H6B109.5
O2—Cr1—O387.51 (5)H6A—C6—H6B109.5
O1—Cr1—O3177.84 (5)N4—C6—H6C109.5
O2—Cr1—N2176.74 (5)H6A—C6—H6C109.5
O1—Cr1—N290.76 (4)H6B—C6—H6C109.5
O3—Cr1—N290.76 (5)N6—C10—H10A109.5
O2—Cr1—N198.71 (5)N6—C10—H10B109.5
O1—Cr1—N190.80 (5)H10A—C10—H10B109.5
O3—Cr1—N191.00 (5)N6—C10—H10C109.5
N2—Cr1—N178.55 (5)H10A—C10—H10C109.5
O2—Cr1—N3104.47 (5)H10B—C10—H10C109.5
O1—Cr1—N389.56 (5)Cr1—O3—H45118.6 (17)
O3—Cr1—N389.24 (5)Cr1—O3—H46115.2 (16)
N2—Cr1—N378.26 (5)H45—O3—H46113 (2)
N1—Cr1—N3156.81 (5)N3—C31—C32121.40 (14)
O5—Cl1—O4109.71 (8)N3—C31—C25114.47 (13)
O5—Cl1—O6110.08 (7)C32—C31—C25124.13 (14)
O4—Cl1—O6109.53 (8)N2—C25—C24120.25 (14)
O5—Cl1—O7109.29 (7)N2—C25—C31113.06 (12)
O4—Cl1—O7109.49 (7)C24—C25—C31126.68 (14)
O6—Cl1—O7108.72 (7)C23—C22—C21118.31 (14)
O11—Cl2—O9110.99 (9)C23—C22—H22120.8
O11—Cl2—O10109.01 (10)C21—C22—H22120.8
O9—Cl2—O10109.30 (10)C33—C34—C35119.05 (15)
O11—Cl2—O8109.39 (9)C33—C34—H34120.5
O9—Cl2—O8109.83 (9)C35—C34—H34120.5
O10—Cl2—O8108.27 (8)C12—C13—C14119.61 (15)
C4—O1—Cr1127.56 (9)C12—C13—H13120.2
C2—O2—Cr1128.13 (9)C14—C13—H13120.2
C25—N2—C21122.11 (13)N1—C15—C14121.21 (14)
C25—N2—Cr1119.10 (10)N1—C15—C21114.15 (13)
C21—N2—Cr1118.71 (10)C14—C15—C21124.63 (14)
C35—N3—C31119.02 (13)C25—C24—C23118.39 (14)
C35—N3—Cr1125.91 (10)C25—C24—H24120.8
C31—N3—Cr1115.07 (10)C23—C24—H24120.8
C11—N1—C15119.14 (13)C15—C14—C13119.07 (15)
C11—N1—Cr1125.54 (10)C15—C14—H14120.5
C15—N1—Cr1115.32 (10)C13—C14—H14120.5
O12—P1—N4110.15 (7)C13—C12—C11118.86 (15)
O12—P1—N6107.93 (7)C13—C12—H12120.6
N4—P1—N6111.59 (7)C11—C12—H12120.6
O12—P1—N5115.13 (7)O2—C2—C3124.09 (13)
N4—P1—N5103.19 (7)O2—C2—C1114.96 (13)
N6—P1—N5108.85 (7)C3—C2—C1120.94 (14)
C7—N4—C6113.68 (13)O1—C4—C3124.53 (13)
C7—N4—P1120.14 (11)O1—C4—C5115.50 (13)
C6—N4—P1124.59 (11)C3—C4—C5119.97 (13)
C9—N5—C8113.07 (14)C2—C3—C4124.34 (14)
C9—N5—P1121.76 (12)C2—C3—H3117.8
C8—N5—P1116.98 (11)C4—C3—H3117.8
H5A—O13—H5B109 (2)N2—C21—C22120.24 (14)
H4B—O14—H4A110 (3)N2—C21—C15113.14 (12)
C10—N6—C17114.10 (14)C22—C21—C15126.62 (14)
C10—N6—P1122.88 (12)C4—C5—H5C109.5
C17—N6—P1121.96 (12)C4—C5—H5D109.5
N4—C7—H7A109.5H5C—C5—H5D109.5
N4—C7—H7B109.5C4—C5—H5E109.5
H7A—C7—H7B109.5H5C—C5—H5E109.5
N4—C7—H7C109.5H5D—C5—H5E109.5
H7A—C7—H7C109.5C31—C32—C33119.22 (15)
H7B—C7—H7C109.5C31—C32—H32120.4
N5—C8—H8A109.5C33—C32—H32120.4
N5—C8—H8B109.5C34—C33—C32119.33 (15)
H8A—C8—H8B109.5C34—C33—H33120.3
N5—C8—H8C109.5C32—C33—H33120.3
H8A—C8—H8C109.5N3—C35—C34121.97 (14)
H8B—C8—H8C109.5N3—C35—H35119
N5—C9—H9A109.5C34—C35—H35119
N5—C9—H9B109.5N1—C11—C12122.09 (15)
H9A—C9—H9B109.5N1—C11—H11119
N5—C9—H9C109.5C12—C11—H11119
H9A—C9—H9C109.5C22—C23—C24120.68 (14)
H9B—C9—H9C109.5C22—C23—H23119.7
N6—C17—H17A109.5C24—C23—H23119.7
N6—C17—H17B109.5C2—C1—H1A109.5
H17A—C17—H17B109.5C2—C1—H1B109.5
N6—C17—H17C109.5H1A—C1—H1B109.5
H17A—C17—H17C109.5C2—C1—H1C109.5
H17B—C17—H17C109.5H1A—C1—H1C109.5
N4—C6—H6A109.5H1B—C1—H1C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O14—H4A···O100.86 (3)2.00 (3)2.838 (2)163 (3)
O14—H4B···O8i0.80 (3)2.09 (3)2.861 (2)162 (2)
O3—H45···O130.72 (2)1.93 (2)2.6461 (17)171 (2)
C1—H1A···O13ii0.962.773.384 (2)123
C6—H6A···N50.962.523.007 (2)111
C7—H7A···O120.962.472.976 (2)113
C9—H9A···N60.962.543.043 (2)113
C13—H13···O13iii0.932.483.289 (2)145
O14—H4A···O100.86 (3)2.00 (3)2.838 (2)163 (3)
O14—H4B···O8i0.80 (3)2.09 (3)2.861 (2)162 (2)
O3—H45···O130.72 (2)1.93 (2)2.6461 (17)171 (2)
C1—H1A···O13ii0.962.773.384 (2)123
C6—H6A···N50.962.523.007 (2)111
C7—H7A···O120.962.472.976 (2)113
C9—H9A···N60.962.543.043 (2)113
C13—H13···O13iii0.932.483.289 (2)145
C17—H17A···O120.962.492.970 (2)111
O13—H5A···O7iii0.75 (3)2.14 (3)2.8830 (18)172 (3)
O13—H5B···O14iv0.89 (3)1.84 (3)2.7356 (19)177 (2)
O3—H46···O12v0.87 (3)1.63 (3)2.4989 (16)175 (3)
C6—H6C···O9vi0.962.573.466 (2)155
C11—H11···O6iii0.932.593.322 (2)136
C14—H14···O6vii0.932.483.199 (2)134
C22—H22···O4vii0.932.473.367 (2)163
C24—H24···O8viii0.932.533.415 (2)159
C32—H32···O14ix0.932.573.289 (2)135
C35—H35···O70.932.513.3811 (19)156
C17—H17A···O120.962.492.970 (2)111
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x+3/2, y+1/2, −z+1/2; (v) x, y, z−1; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) x−1/2, −y+3/2, z−1/2; (ix) −x+1, −y+1, −z.
Selected geometric parameters (Å, °) top
Cr1—O21.9268 (10)Cr1—N21.9976 (12)
Cr1—O11.9356 (10)Cr1—N12.0547 (12)
Cr1—O31.9684 (11)Cr1—N32.0676 (12)
O2—Cr1—O191.05 (4)N2—Cr1—N178.55 (5)
O2—Cr1—O387.51 (5)N2—Cr1—N378.26 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O14—H4A···O100.86 (3)2.00 (3)2.838 (2)163 (3)
O14—H4B···O8i0.80 (3)2.09 (3)2.861 (2)162 (2)
O3—H45···O130.72 (2)1.93 (2)2.6461 (17)171 (2)
O13—H5A···O7ii0.75 (3)2.14 (3)2.8830 (18)172 (3)
O13—H5B···O14iii0.89 (3)1.84 (3)2.7356 (19)177 (2)
O3—H46···O12iv0.87 (3)1.63 (3)2.4989 (16)175 (3)
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x, y, z−1.
Acknowledgements top

Financial assistance from the South African National Research Foundation (NRF), the Research Fund of the University of the Free State and SASOL is gratefully acknowledged. Part of this material is based on work supported by the South African National Research Foundation (GUN 2038915). Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NRF.

references
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