(2,2-Bipyridyl N,N′-dioxide-κ²O,O′)trichloridobis(methanol-κO)terbium(III)

In the title complex, [TbCl₃(C₁₀H₁₂N₂O₂)(CH₄O)₂], each Tb^III ion is seven-coordinate in a pentagonal-bipyramidal coordination geometry. A crystallographic twofold rotation axis passes through Tb and one Cl atom.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](O-C) = 0.014 Å
• R factor = 0.039
• wR factor = 0.073
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Tb1

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.25
           From the CIF: _reflns_number_total               1480
           Count of symmetry unique reflns          891
           Completeness (_total/calc)            166.11%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       589
           Fraction of Friedel pairs measured     0.661
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Tb1         (3)       3.20
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         76

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Lanthanide complexes have been investigated intensively because of their potential application in various optical devices [Ropp et al., 2004; McGehee et al., 1999; Tsaryuk et al., 2003]. As shown in Fig.1, in the title compound the Tb^III ion are coordinated to three Cl atoms and four O atoms which belong to a 2,2-bipyridyl-N,N'-dioxide molecule and two methanol molecules, respectively in a distorted pentagonal bipyramid geometry, with atom O2 O2A O1 O1A and Cl2 locating at equatorial positions. The crystal structure of (I) contains extensive hydrogen bonding. Neighbouring molecules are connected to each other mainly via O(2)—H(7)···Cl(2)⁽ⁱ⁾ hydrogen bonds [symmetry code: (i) is -x + 2,-y,z + 1/2], the sum of the angles and bond length of d(D···A) about O(2)—H(7)···Cl(2)⁽ⁱ⁾ are 128 (10)/% and 3.179 (8) A/%,respectively.

Related literature

For related literature, see: McGehee et al. (1999); Ropp (2004); Tsaryuk et al. (2003).

S2. Experimental

A mixture of 2,2-bipyridyl-N,N'-dioxide (0.182 g, 0.001 mol), TbCl₃6H₂O (0.374 g, 0.1 mol) was added to 30 ml me thanol, The mixture was heated at 350 K or so for 5 h under reflux with stirring.The resulting solution was then filtered off. Single crystals suitable for X-ray diffraction analysis formed after a week by slow evaporation of the solvent.

S3. Refinement

The H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H distances of 0.93 Å (pyridine ring), 0.86 Å (amine group) and 0.96 Å (methyl), and with U_iso(H) 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
	Fig. 2. The packing diagram of (I), viewed along the z axis; hydrogen bonds are shown as dashed lines.

(2,2-Bipyridyl N,N'-dioxide-κ²O,O')trichloridobis(methanol-κO)terbium(III)

Crystal data

[TbCl3(C10H12N2O2)(CH4O)2]	Z = 4
Mr = 517.54	F(000) = 1000
Orthorhombic, C2221	Dx = 2.047 Mg m^−3
Hall symbol: C 2c 2	Mo Kα radiation, λ = 0.71073 Å
a = 13.985 (4) Å	µ = 4.71 mm^−1
b = 15.054 (4) Å	T = 298 K
c = 7.976 (2) Å	Block, yellow
V = 1679.2 (8) Å^3	0.20 × 0.13 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1480 independent reflections
Radiation source: fine-focus sealed tube	1156 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
φ and ω scans	θmax = 25.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.453, Tmax = 0.595	k = −18→18
4917 measured reflections	l = −9→9

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.018P)^2 + 0.004P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max = 0.002
S = 0.98	Δρmax = 0.94 e Å^−3
1480 reflections	Δρmin = −1.22 e Å^−3
95 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
76 restraints	Extinction coefficient: 0.00061 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with how many Friedel pairs?
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.06 (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
Cl1	0.7799 (2)	0.15435 (17)	−0.1542 (4)	0.0439 (7)
N3	0.5828 (3)	0.0943 (3)	0.0755 (7)	0.0290 (10)
C5	0.5081 (4)	0.0484 (3)	−0.0001 (9)	0.0292 (11)
C4	0.4313 (3)	0.0947 (4)	−0.0678 (8)	0.0308 (12)
H4	0.3814	0.0640	−0.1184	0.037*
C3	0.4292 (3)	0.1869 (4)	−0.0600 (8)	0.0320 (12)
H3	0.3778	0.2179	−0.1053	0.038*
C2	0.5039 (4)	0.2328 (3)	0.0156 (9)	0.0315 (12)
H2	0.5025	0.2945	0.0208	0.038*
C1	0.5807 (3)	0.1865 (3)	0.0834 (8)	0.0302 (11)
H1	0.6307	0.2172	0.1339	0.036*
O1	0.6523 (4)	0.0482 (4)	0.1438 (8)	0.0287 (11)
Tb1	0.78927 (4)	0.0000	0.0000	0.0237 (2)
O2	0.8425 (6)	0.0574 (6)	0.2615 (10)	0.0487 (19)
C7	0.8075 (8)	0.1191 (8)	0.3768 (13)	0.052 (2)
H7A	0.8356	0.1082	0.4847	0.077*
H7B	0.7393	0.1136	0.3847	0.077*
H7C	0.8236	0.1781	0.3404	0.077*
Cl2	0.9862 (2)	0.0000	0.0000	0.0493 (9)
H7	0.860 (8)	0.013 (11)	0.320 (13)	0.08 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0432 (16)	0.0358 (14)	0.0528 (18)	−0.0030 (15)	0.0040 (16)	0.0116 (12)
N3	0.0264 (18)	0.027 (2)	0.033 (2)	0.0045 (17)	0.0051 (18)	−0.0006 (19)
C5	0.027 (2)	0.028 (2)	0.033 (3)	0.0028 (18)	0.005 (2)	0.000 (2)
C4	0.029 (2)	0.030 (2)	0.034 (3)	0.004 (2)	0.004 (2)	0.001 (2)
C3	0.030 (2)	0.030 (2)	0.035 (3)	0.005 (2)	0.005 (2)	0.001 (2)
C2	0.031 (2)	0.028 (2)	0.036 (3)	0.0040 (19)	0.006 (2)	0.001 (2)
C1	0.028 (2)	0.027 (2)	0.035 (3)	0.0028 (19)	0.006 (2)	−0.001 (2)
O1	0.0264 (19)	0.027 (2)	0.033 (3)	0.0063 (18)	0.0041 (17)	−0.002 (2)
Tb1	0.0189 (3)	0.0285 (3)	0.0238 (3)	0.000	0.000	−0.0023 (7)
O2	0.041 (3)	0.069 (5)	0.036 (3)	0.024 (4)	−0.013 (3)	−0.025 (3)
C7	0.043 (4)	0.070 (6)	0.041 (4)	0.024 (4)	−0.013 (4)	−0.027 (3)
Cl2	0.0222 (12)	0.083 (3)	0.042 (2)	0.000	0.000	0.000 (5)

Geometric parameters (Å, º)

Cl1—Tb1	2.632 (3)	C1—H1	0.9300
N3—O1	1.312 (7)	O1—Tb1	2.347 (6)
N3—C5	1.3900	Tb1—O1^i	2.347 (6)
N3—C1	1.3900	Tb1—O2	2.377 (7)
C5—C4	1.3900	Tb1—O2^i	2.377 (7)
C5—C5^i	1.4572	Tb1—Cl1^i	2.632 (3)
C4—C3	1.3900	Tb1—Cl2	2.754 (3)
C4—H4	0.9300	O2—C7	1.396 (12)
C3—C2	1.3900	O2—H7	0.85 (14)
C3—H3	0.9300	C7—H7A	0.9600
C2—C1	1.3900	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
O1—N3—C5	118.3 (5)	O1^i—Tb1—Cl1	90.21 (17)
O1—N3—C1	121.7 (5)	O1—Tb1—Cl1	85.13 (17)
C5—N3—C1	120.0	O2—Tb1—Cl1	96.0 (2)
N3—C5—C4	120.0	O2^i—Tb1—Cl1	85.8 (2)
N3—C5—C5^i	119.8 (5)	O1^i—Tb1—Cl1^i	85.13 (17)
C4—C5—C5^i	120.1 (5)	O1—Tb1—Cl1^i	90.21 (17)
C3—C4—C5	120.0	O2—Tb1—Cl1^i	85.8 (2)
C3—C4—H4	120.0	O2^i—Tb1—Cl1^i	96.0 (2)
C5—C4—H4	120.0	Cl1—Tb1—Cl1^i	174.30 (14)
C4—C3—C2	120.0	O1^i—Tb1—Cl2	144.69 (16)
C4—C3—H3	120.0	O1—Tb1—Cl2	144.69 (16)
C2—C3—H3	120.0	O2—Tb1—Cl2	71.7 (2)
C1—C2—C3	120.0	O2^i—Tb1—Cl2	71.7 (2)
C1—C2—H2	120.0	Cl1—Tb1—Cl2	92.85 (7)
C3—C2—H2	120.0	Cl1^i—Tb1—Cl2	92.85 (7)
C2—C1—N3	120.0	C7—O2—Tb1	135.3 (7)
C2—C1—H1	120.0	C7—O2—H7	105 (9)
N3—C1—H1	120.0	Tb1—O2—H7	107 (10)
N3—O1—Tb1	124.4 (5)	O2—C7—H7A	109.5
O1^i—Tb1—O1	70.6 (3)	O2—C7—H7B	109.5
O1^i—Tb1—O2	142.8 (3)	H7A—C7—H7B	109.5
O1—Tb1—O2	73.4 (3)	O2—C7—H7C	109.5
O1^i—Tb1—O2^i	73.4 (3)	H7A—C7—H7C	109.5
O1—Tb1—O2^i	142.8 (3)	H7B—C7—H7C	109.5
O2—Tb1—O2^i	143.5 (4)

Symmetry code: (i) x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H7···Cl2^ii	0.85 (9)	2.59 (9)	3.179 (8)	128 (10)

Symmetry code: (ii) −x+2, −y, z+1/2.