Redetermination of cis-di­acetonitrile­bis­(2,2'-bipyridine)ruthenium(II) hexa­fluoro­phosphate

The title compound, [Ru(C₁₀H₈N₂)₂(CH₃CN)₂](PF₆)₂, a six-coordinate ruthenium(II) complex, crystallizes in the monoclinic C2/c space group showing different symmetry from the previously reported P2₁/n. A crystallographic twofold rotation axis passes through the Ru atom. The two C atoms and H atoms of one acetonitrile ligand are disordered over two positions, with site occupancy factors of ca 0.55 and 0.45. Three F atoms are disordered over two positions, with similar site occupancy factors.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in main residue
• R factor = 0.048
• wR factor = 0.098
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ru1
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         F4
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for         F6
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         F2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         F3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        F3'
PLAT301_ALERT_3_C Main Residue  Disorder .........................      11.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      30.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C3     ..  C12'    ..       3.18 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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S1. Comment

The structures of cis-bis(acetonitrile)bis(2,2'-bipyridine) ruthenium(II) diperchlorate (Chattopadhyay et al., 2004), trans-bis(acetonitrile)bis(2,2'-bipyridine) ruthenium(II) diperchlorate (Cordes et al., 1992), and the title complex (Heeg et al., 1985) have been reported previously. We present herein the crystal structure of the title compound (I) again with the same unit cell as Heeg et al.'s within the experimental error, but it crystallizes in the monoclinic C2/c space group other than the earlier P2₁/n.

The atom-numbering scheme of compound (I) is shown in Fig.1, while selected bond distances and angles are given in Table 1. The Ru—N bond lengths and bond angles are comparable with those in literature. The presence of acetonitrile molecules in this Ru(II) complex can be verified by routine characterization. The main difference between our data and Heeg et al.'s is the assignment of the space group. Our results demonstrate the higher symmetry of molecule (C2/c instead of P2₁/n), and two carbon atoms of monodentate acetonitrile molecules are refined disorderly. We failed to solve this structure by assigning the reported P2₁/n space group.

Related literature

For the earlier report of this crystal structure, see: Heeg et al. (1985). For analogous complexes, see: Chattopadhyay et al. (2004); Cordes et al. (1992).

S2. Experimental

The title complex (I) was obtained by refluxing equal molar ratio of Ru(bpy)₂Cl₂.H₂O (0.02 g, 0.04 mmol) and a pre-synthesized schiff base, 4-[2-(pyridin-4-ylimino)-ethyl]-benzoic acid (0.01 g, 0.04 mmol) in 30 ml acetonitrile for 1 h. The mixture was cooled to room temperature and a 10 ml saturated NH₄PF₆ solution was added. Orange single-crystal of (I) suitable for the X-ray diffraction analysis was grown directly from the mother liquor as a by-product. Elemental analysis, calculated for RuC₂₄H₂₂N₆P₂F₁₂: C, 36.70; H, 2.82; N, 10.70%; found: C, 36.55; H, 2.99; N, 10.48%. IR (KBr): 3123, 3094, 3003, 2938, 1606, 1468, 1449, 1314, 1276, 1243, 1164, 1040, 833, 762, and 557 cm^{-1. 1}H NMR (d₆-DMSO): δ (p.p.m.) 9.364 (2H), 8.778 (2H), 8.649 (2H), 8.353 (2H), 8.031 (2H), 7.931 (2H), 7.575 (2H), 7.373 (2H), 2.437 (6H).

S3. Refinement

The non-hydrogen atoms were refined anisotropically, whereas the H atoms were placed in geometrically idealized positions (C—H = 0.93–0.96 Å) and refined as riding atoms, with U_iso(H) = 1.5U_eq(for methyl C) or U_iso(H) = 1.2U_eq(C) for the other C atoms. F2, F3 and F6 atoms of hexafluorophosphate are refined over two sites with 0.557 (17):0.443 (17) site occupancy factors. Due to the disorder of acetonitrile molecules, the 'similar U^ij' restraints (SIMU) were used to restrain the U^ij components of neighboring atoms (N3—C11 and N3—C11', six for each). The effective standard deviations is set as 0.004 for N3—C11 and 0.003 for N3—C11', respectively.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A drawing of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and the H atoms are omitted for clarity.

cis-diacetonitrilebis(2,2'-bipyridine)ruthenium(II) hexafluorophosphate

Crystal data

[Ru(C10H8N2)2(C2H3N)2](F6P)2	F(000) = 1560
Mr = 785.49	Dx = 1.739 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1829 reflections
a = 17.2499 (18) Å	θ = 2.3–19.1°
b = 10.5008 (11) Å	µ = 0.73 mm^−1
c = 16.6600 (17) Å	T = 291 K
β = 96.201 (2)°	Block, orange
V = 3000.1 (5) Å^3	0.16 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2641 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −20→18
Tmin = 0.892, Tmax = 0.931	k = −9→12
7231 measured reflections	l = −19→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0345P)^2 + 1.566P] where P = (Fo^2 + 2Fc^2)/3
2641 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.54 e Å^−3
12 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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)
Ru1	0.0000	0.97826 (5)	0.7500	0.0657 (2)
C1	0.0270 (3)	1.1608 (4)	0.8777 (3)	0.0689 (12)
C2	0.0579 (4)	1.2636 (5)	0.9204 (3)	0.1081 (19)
H2	0.0346	1.2943	0.9644	0.130*
C3	0.1238 (5)	1.3207 (6)	0.8976 (4)	0.147 (3)
H3	0.1459	1.3898	0.9266	0.177*
C4	0.1562 (4)	1.2770 (7)	0.8338 (4)	0.145 (3)
H4	0.2005	1.3153	0.8174	0.174*
C5	0.1225 (3)	1.1744 (6)	0.7932 (3)	0.0982 (17)
H5	0.1456	1.1433	0.7492	0.118*
C6	−0.0394 (3)	1.0877 (4)	0.8992 (3)	0.0652 (12)
C7	−0.0783 (3)	1.1116 (5)	0.9658 (3)	0.0906 (15)
H7	−0.0651	1.1818	0.9985	0.109*
C8	−0.1358 (3)	1.0317 (7)	0.9831 (3)	0.1064 (19)
H8	−0.1619	1.0462	1.0282	0.128*
C9	−0.1549 (3)	0.9330 (7)	0.9356 (3)	0.120 (2)
H9	−0.1944	0.8777	0.9470	0.144*
C10	−0.1151 (3)	0.9134 (6)	0.8687 (3)	0.1113 (19)
H10	−0.1285	0.8435	0.8357	0.134*
C11	0.1279 (11)	0.7826 (11)	0.8336 (6)	0.115 (3)	0.546 (11)
C12	0.1854 (8)	0.6918 (10)	0.8694 (6)	0.109 (5)	0.546 (11)
H12A	0.2363	0.7293	0.8712	0.163*	0.546 (11)
H12B	0.1744	0.6717	0.9232	0.163*	0.546 (11)
H12C	0.1837	0.6154	0.8376	0.163*	0.546 (11)
C11'	0.0731 (12)	0.7344 (15)	0.8298 (8)	0.120 (2)	0.454 (11)
C12'	0.1042 (13)	0.6169 (14)	0.8608 (8)	0.141 (9)	0.454 (11)
H12D	0.0652	0.5539	0.8676	0.212*	0.454 (11)
H12E	0.1392	0.5854	0.8244	0.212*	0.454 (11)
H12F	0.1330	0.6351	0.9122	0.212*	0.454 (11)
F1	0.6154 (3)	0.8889 (5)	0.6588 (3)	0.220 (3)
F2	0.7125 (6)	1.035 (2)	0.5688 (7)	0.183 (7)	0.559 (18)
F3	0.7302 (9)	0.9507 (18)	0.6692 (13)	0.203 (8)	0.559 (18)
F4	0.6351 (8)	1.0821 (9)	0.6847 (6)	0.384 (7)
F5	0.5853 (3)	1.0436 (9)	0.5748 (5)	0.288 (4)
F6	0.7016 (15)	0.887 (2)	0.587 (2)	0.326 (13)	0.559 (18)
F2'	0.6890 (14)	1.1222 (15)	0.5882 (13)	0.180 (9)	0.441 (18)
F3'	0.7146 (12)	1.006 (3)	0.7012 (8)	0.187 (11)	0.441 (18)
F6'	0.6389 (14)	0.9189 (12)	0.5469 (6)	0.168 (8)	0.441 (18)
N1	0.0599 (2)	1.1177 (3)	0.8125 (2)	0.0642 (9)
N2	−0.0591 (2)	0.9896 (3)	0.8497 (2)	0.0687 (10)
N3	0.0682 (3)	0.8417 (4)	0.8050 (2)	0.1189 (17)
P1	0.65715 (12)	0.9967 (2)	0.62417 (10)	0.1139 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0907 (4)	0.0551 (3)	0.0515 (3)	0.000	0.0074 (3)	0.000
C1	0.085 (4)	0.057 (3)	0.061 (3)	0.000 (3)	−0.008 (3)	0.000 (2)
C2	0.166 (6)	0.082 (4)	0.074 (4)	−0.031 (4)	0.005 (4)	−0.012 (3)
C3	0.218 (8)	0.130 (6)	0.089 (5)	−0.103 (6)	−0.004 (5)	−0.003 (4)
C4	0.155 (6)	0.197 (8)	0.078 (5)	−0.096 (6)	−0.013 (5)	0.013 (5)
C5	0.084 (4)	0.144 (5)	0.064 (3)	−0.033 (4)	−0.006 (3)	0.009 (3)
C6	0.075 (3)	0.064 (3)	0.056 (3)	0.011 (3)	0.003 (2)	0.005 (2)
C7	0.107 (4)	0.096 (4)	0.071 (4)	0.021 (4)	0.015 (3)	−0.005 (3)
C8	0.088 (4)	0.159 (6)	0.075 (4)	0.011 (4)	0.021 (3)	0.016 (4)
C9	0.094 (4)	0.193 (7)	0.074 (4)	−0.050 (5)	0.012 (4)	0.019 (4)
C10	0.135 (5)	0.132 (5)	0.069 (4)	−0.059 (4)	0.016 (4)	−0.002 (3)
C11	0.205 (7)	0.081 (5)	0.061 (4)	0.052 (4)	0.028 (5)	0.010 (4)
C12	0.146 (12)	0.082 (8)	0.099 (8)	0.034 (8)	0.013 (7)	0.020 (6)
C11'	0.213 (6)	0.087 (4)	0.063 (4)	0.059 (4)	0.028 (4)	0.012 (3)
C12'	0.22 (2)	0.096 (11)	0.115 (11)	0.073 (13)	0.047 (12)	0.043 (9)
F1	0.222 (5)	0.218 (5)	0.208 (5)	−0.120 (4)	−0.027 (4)	0.087 (4)
F2	0.142 (7)	0.30 (2)	0.126 (7)	0.003 (13)	0.080 (6)	0.050 (12)
F3	0.191 (11)	0.197 (13)	0.198 (16)	0.025 (9)	−0.082 (11)	0.049 (11)
F4	0.569 (16)	0.342 (11)	0.225 (8)	0.239 (12)	−0.031 (10)	−0.106 (8)
F5	0.146 (4)	0.454 (12)	0.262 (7)	0.016 (6)	0.007 (5)	0.195 (8)
F6	0.228 (19)	0.34 (2)	0.42 (3)	0.023 (18)	0.09 (2)	−0.14 (2)
F2'	0.217 (19)	0.117 (10)	0.193 (15)	−0.078 (10)	−0.044 (12)	0.073 (9)
F3'	0.181 (15)	0.29 (2)	0.084 (7)	−0.153 (17)	0.000 (8)	−0.019 (9)
F6'	0.26 (2)	0.150 (9)	0.084 (7)	0.009 (11)	−0.018 (8)	−0.029 (6)
N1	0.068 (3)	0.069 (2)	0.054 (2)	−0.006 (2)	−0.0019 (19)	0.0053 (18)
N2	0.081 (3)	0.072 (3)	0.053 (2)	−0.017 (2)	0.0063 (19)	0.0030 (19)
N3	0.213 (5)	0.085 (3)	0.061 (2)	0.061 (3)	0.027 (3)	0.012 (2)
P1	0.1182 (15)	0.1435 (18)	0.0797 (11)	−0.0289 (14)	0.0096 (12)	0.0056 (12)

Geometric parameters (Å, º)

Ru1—N3^i	2.012 (4)	C9—C10	1.387 (7)
Ru1—N3	2.012 (4)	C9—H9	0.9300
Ru1—N1	2.016 (3)	C10—N2	1.319 (6)
Ru1—N1^i	2.016 (3)	C10—H10	0.9300
Ru1—N2	2.045 (3)	C11—N3	1.251 (14)
Ru1—N2^i	2.045 (3)	C11—C12	1.456 (13)
C1—N1	1.358 (5)	C12—H12A	0.9599
C1—C2	1.369 (6)	C12—H12B	0.9601
C1—C6	1.455 (6)	C12—H12C	0.9600
C2—C3	1.375 (8)	C11'—N3	1.200 (15)
C2—H2	0.9300	C11'—C12'	1.421 (15)
C3—C4	1.335 (9)	C12'—H12D	0.9600
C3—H3	0.9300	C12'—H12E	0.9600
C4—C5	1.368 (7)	C12'—H12F	0.9601
C4—H4	0.9300	F1—P1	1.490 (4)
C5—N1	1.303 (5)	F2—P1	1.455 (10)
C5—H5	0.9300	F3—P1	1.477 (12)
C6—N2	1.340 (5)	F4—P1	1.432 (7)
C6—C7	1.381 (6)	F5—P1	1.495 (5)
C7—C8	1.354 (7)	F6—P1	1.549 (17)
C7—H7	0.9300	F2'—P1	1.571 (11)
C8—C9	1.323 (8)	F3'—P1	1.538 (15)
C8—H8	0.9300	F6'—P1	1.529 (10)
N3^i—Ru1—N3	89.1 (3)	H12A—C12—H12F	145.9
N3^i—Ru1—N1	174.27 (17)	H12C—C12—H12F	86.5
N3—Ru1—N1	92.31 (17)	H12E—C12—H12F	65.8
N3^i—Ru1—N1^i	92.31 (17)	N3—C11'—C12'	161.9 (19)
N3—Ru1—N1^i	174.27 (17)	C11'—C12'—H12C	104.0
N1—Ru1—N1^i	86.83 (19)	C11'—C12'—H12D	113.5
N3^i—Ru1—N2	95.34 (16)	H12C—C12'—H12D	135.4
N3—Ru1—N2	89.42 (15)	C11'—C12'—H12E	108.0
N1—Ru1—N2	79.13 (15)	H12D—C12'—H12E	109.5
N1^i—Ru1—N2	95.98 (15)	C11'—C12'—H12F	106.9
N3^i—Ru1—N2^i	89.42 (15)	H12C—C12'—H12F	80.2
N3—Ru1—N2^i	95.34 (16)	H12D—C12'—H12F	109.5
N1—Ru1—N2^i	95.98 (15)	H12E—C12'—H12F	109.5
N1^i—Ru1—N2^i	79.13 (15)	C5—N1—C1	118.4 (4)
N2—Ru1—N2^i	173.3 (2)	C5—N1—Ru1	126.7 (4)
N1—C1—C2	120.4 (5)	C1—N1—Ru1	114.8 (3)
N1—C1—C6	115.5 (4)	C10—N2—C6	117.6 (4)
C2—C1—C6	124.1 (5)	C10—N2—Ru1	127.0 (3)
C1—C2—C3	119.2 (6)	C6—N2—Ru1	115.4 (3)
C1—C2—H2	120.4	C11'—N3—C11	51.6 (9)
C3—C2—H2	120.4	C11'—N3—Ru1	147.3 (12)
C4—C3—C2	120.0 (6)	C11—N3—Ru1	160.7 (9)
C4—C3—H3	120.0	F4—P1—F2	121.0 (11)
C2—C3—H3	120.0	F4—P1—F3	97.1 (10)
C3—C4—C5	118.2 (6)	F2—P1—F3	80.2 (10)
C3—C4—H4	120.9	F4—P1—F1	91.5 (6)
C5—C4—H4	120.9	F2—P1—F1	146.6 (10)
N1—C5—C4	123.8 (6)	F3—P1—F1	88.7 (6)
N1—C5—H5	118.1	F4—P1—F5	85.0 (6)
C4—C5—H5	118.1	F2—P1—F5	97.0 (6)
N2—C6—C7	121.4 (5)	F3—P1—F5	177.1 (9)
N2—C6—C1	114.1 (4)	F1—P1—F5	93.2 (3)
C7—C6—C1	124.4 (5)	F4—P1—F6'	151.9 (10)
C8—C7—C6	119.3 (5)	F2—P1—F6'	72.8 (13)
C8—C7—H7	120.4	F3—P1—F6'	109.9 (15)
C6—C7—H7	120.4	F1—P1—F6'	81.8 (6)
C9—C8—C7	120.0 (6)	F5—P1—F6'	68.3 (8)
C9—C8—H8	120.0	F4—P1—F3'	64.3 (9)
C7—C8—H8	120.0	F2—P1—F3'	95.9 (8)
C8—C9—C10	118.9 (6)	F1—P1—F3'	91.2 (7)
C8—C9—H9	120.5	F5—P1—F3'	149.1 (12)
C10—C9—H9	120.5	F6'—P1—F3'	142.6 (15)
N2—C10—C9	122.8 (5)	F4—P1—F6	158.4 (15)
N2—C10—H10	118.6	F2—P1—F6	64.1 (9)
C9—C10—H10	118.6	F3—P1—F6	62.0 (18)
N3—C11—C12	167.6 (14)	F1—P1—F6	82.8 (9)
C11—C12—H12A	109.0	F5—P1—F6	116.1 (15)
C11—C12—H12B	109.4	F6'—P1—F6	47.9 (10)
H12A—C12—H12B	109.5	F3'—P1—F6	94.8 (19)
C11—C12—H12C	110.0	F4—P1—F2'	82.7 (11)
H12A—C12—H12C	109.5	F3—P1—F2'	98.8 (9)
H12B—C12—H12C	109.5	F1—P1—F2'	171.1 (11)
C11—C12—H12E	89.0	F5—P1—F2'	79.5 (7)
H12A—C12—H12E	138.1	F6'—P1—F2'	100.1 (11)
H12B—C12—H12E	98.8	F3'—P1—F2'	92.4 (9)
C11—C12—H12F	92.2	F6—P1—F2'	105.0 (12)

Symmetry code: (i) −x, y, −z+3/2.