Crystal structure of an eight-coordinate terbium(III) ion chelated by N,N′-bis­(2-hy­droxy­benz­yl)-N,N′-bis­(pyridin-2-ylmeth­yl)ethyl­enedi­amine (bbpen²⁻) and nitrate

The reaction of terbium(III) nitrate penta­hydrate in aceto­nitrile with N,N′-bis­(2-hy­droxy­benz­yl)-N,N′-bis­(pyridin-2-ylmeth­yl)ethyl­enedi­amine (H₂bbpen), previously deprotonated with tri­ethyl­amine, produced the mononuclear compound [Tb(Cbbpen)(NO₃)]. The mol­ecule lies on a twofold rotation axis and the Tb^III ion is eight-coordinate with a slightly distorted dodeca­hedral coordination geometry.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.010
• wR factor = 0.027
• Data-to-parameter ratio = 18.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.89 Report
PLAT213_ALERT_2_C Atom O3              has ADP max/min Ratio .....        3.7 prolat
PLAT220_ALERT_2_C Large Non-Solvent  O     Ueq(max)/Ueq(min) Range        3.5 Ratio
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         N1 Check
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT033_ALERT_4_G Flack x Value Deviates > 2*sigma from Zero .....     -0.011
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Tb1    --  O2      ..        5.9 su
PLAT791_ALERT_4_G The Model has Chirality at N3      .............          S Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          4 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and WinGX (Farrugia, 2012).

[N,N'-Bis(2-oxidobenzyl-κO)-N,N'-bis(pyridin-2-ylmethyl-κN)ethylenediamine-κ²N,N'](nitrato-κ²O,O')terbium(III)

Crystal data

[Tb(C28H28N4O2)(NO3)]	Dx = 1.686 Mg m^−3
Mr = 673.47	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, C2221	Cell parameters from 9558 reflections
a = 8.5947 (6) Å	θ = 2.9–28.3°
b = 18.2401 (17) Å	µ = 2.71 mm^−1
c = 16.9272 (13) Å	T = 100 K
V = 2653.6 (4) Å^3	Prism, pale pink
Z = 4	0.43 × 0.20 × 0.20 mm
F(000) = 1344

Data collection

Bruker D8 Venture/Photon 100 CMOS diffractometer	3320 independent reflections
Radiation source: fine-focus sealed tube	3289 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 10.4167 pixels mm^-1	θmax = 28.4°, θmin = 2.9°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS2014/2; Bruker, 2014)	k = −24→24
Tmin = 0.581, Tmax = 0.746	l = −22→22
75009 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.010	w = 1/[σ^2(Fo^2) + (0.0139P)^2 + 1.0428P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.027	(Δ/σ)max = 0.004
S = 1.15	Δρmax = 0.87 e Å^−3
3320 reflections	Δρmin = −0.30 e Å^−3
178 parameters	Absolute structure: Flack x determined using 1431 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons & Flack, 2004)
0 restraints	Absolute structure parameter: −0.0107 (19)
Primary atom site location: structure-invariant direct methods

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tb1	0.5000	0.51826 (2)	0.2500	0.01172 (4)
O1	0.59854 (16)	0.54526 (8)	0.13398 (8)	0.0167 (3)
O2	0.4357 (2)	0.39605 (9)	0.30473 (10)	0.0312 (4)
O3	0.5000	0.29285 (11)	0.2500	0.0586 (9)
N1	0.5000	0.35974 (11)	0.2500	0.0293 (6)
N2	0.7540 (2)	0.49068 (9)	0.32221 (10)	0.0183 (3)
N3	0.66305 (19)	0.63257 (8)	0.27777 (9)	0.0130 (3)
C1	0.8272 (3)	0.42575 (12)	0.32538 (14)	0.0249 (4)
H1	0.7809	0.3851	0.2993	0.030*
C2	0.9672 (2)	0.41490 (13)	0.36483 (14)	0.0275 (5)
H2	1.0155	0.3681	0.3656	0.033*
C3	1.0342 (2)	0.47389 (13)	0.40282 (14)	0.0253 (5)
H3	1.1304	0.4685	0.4298	0.030*
C4	0.9590 (2)	0.54124 (13)	0.40111 (12)	0.0203 (4)
H4	1.0022	0.5823	0.4278	0.024*
C5	0.8200 (2)	0.54783 (11)	0.35990 (10)	0.0151 (3)
C6	0.7349 (2)	0.62034 (12)	0.35643 (12)	0.0160 (4)
H6A	0.6528	0.6212	0.3975	0.019*
H6B	0.8088	0.6606	0.3679	0.019*
C7	0.5652 (2)	0.69987 (10)	0.28069 (12)	0.0156 (3)
H7A	0.6323	0.7432	0.2719	0.019*
H7B	0.5190	0.7043	0.3340	0.019*
C8	0.7933 (2)	0.64051 (11)	0.21953 (12)	0.0162 (4)
H8A	0.8566	0.5952	0.2212	0.019*
H8B	0.8607	0.6814	0.2372	0.019*
C9	0.7479 (2)	0.65450 (12)	0.13510 (12)	0.0161 (4)
C10	0.6559 (2)	0.60220 (10)	0.09514 (11)	0.0155 (4)
C11	0.6273 (2)	0.61288 (12)	0.01400 (12)	0.0188 (4)
H11	0.5663	0.5782	−0.0142	0.023*
C12	0.6873 (3)	0.67359 (13)	−0.02515 (12)	0.0232 (4)
H12	0.6664	0.6801	−0.0798	0.028*
C13	0.7777 (3)	0.72492 (13)	0.01476 (14)	0.0251 (4)
H13	0.8186	0.7663	−0.0123	0.030*
C14	0.8073 (2)	0.71496 (11)	0.09491 (12)	0.0199 (4)
H14	0.8688	0.7498	0.1225	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb1	0.01260 (5)	0.01031 (5)	0.01225 (5)	0.000	0.00008 (7)	0.000
O1	0.0177 (6)	0.0180 (6)	0.0145 (6)	−0.0021 (5)	0.0023 (5)	−0.0009 (5)
O2	0.0439 (9)	0.0209 (7)	0.0287 (8)	−0.0086 (7)	−0.0077 (7)	0.0083 (6)
O3	0.096 (2)	0.0096 (8)	0.0704 (19)	0.000	−0.046 (3)	0.000
N1	0.0418 (14)	0.0119 (9)	0.0343 (13)	0.000	−0.028 (2)	0.000
N2	0.0170 (8)	0.0191 (8)	0.0188 (8)	0.0028 (7)	−0.0021 (6)	0.0002 (6)
N3	0.0124 (7)	0.0136 (7)	0.0128 (6)	0.0003 (6)	−0.0002 (5)	0.0006 (5)
C1	0.0244 (10)	0.0208 (10)	0.0294 (11)	0.0046 (8)	−0.0059 (9)	−0.0027 (8)
C2	0.0250 (14)	0.0275 (10)	0.0298 (10)	0.0106 (8)	−0.0037 (8)	0.0042 (8)
C3	0.0180 (13)	0.0364 (11)	0.0214 (9)	0.0023 (8)	−0.0036 (7)	0.0102 (8)
C4	0.0176 (11)	0.0282 (10)	0.0153 (8)	−0.0033 (7)	−0.0028 (6)	0.0061 (8)
C5	0.0147 (8)	0.0196 (9)	0.0110 (8)	0.0001 (7)	0.0013 (6)	0.0032 (7)
C6	0.0162 (9)	0.0181 (9)	0.0138 (9)	−0.0009 (8)	−0.0022 (7)	−0.0010 (8)
C7	0.0161 (8)	0.0110 (8)	0.0198 (8)	−0.0006 (7)	−0.0002 (7)	−0.0012 (7)
C8	0.0124 (8)	0.0210 (9)	0.0153 (8)	−0.0023 (7)	0.0007 (7)	0.0021 (7)
C9	0.0136 (9)	0.0209 (10)	0.0139 (9)	0.0017 (8)	0.0009 (7)	0.0012 (8)
C10	0.0130 (8)	0.0175 (9)	0.0158 (8)	0.0028 (7)	0.0024 (7)	0.0001 (7)
C11	0.0181 (9)	0.0231 (10)	0.0153 (9)	0.0024 (8)	0.0000 (7)	−0.0021 (8)
C12	0.0266 (11)	0.0286 (11)	0.0142 (9)	0.0029 (9)	−0.0004 (8)	0.0042 (8)
C13	0.0303 (11)	0.0238 (10)	0.0210 (11)	−0.0032 (9)	0.0013 (9)	0.0080 (8)
C14	0.0196 (9)	0.0208 (9)	0.0194 (10)	−0.0012 (8)	0.0002 (8)	0.0022 (8)

Geometric parameters (Å, º)

Tb1—O1^i	2.1947 (13)	C3—H3	0.9500
Tb1—O1	2.1947 (13)	C4—C5	1.389 (3)
Tb1—O2^i	2.4764 (15)	C4—H4	0.9500
Tb1—O2	2.4764 (15)	C5—C6	1.513 (3)
Tb1—N2^i	2.5521 (17)	C6—H6A	0.9900
Tb1—N2	2.5521 (17)	C6—H6B	0.9900
Tb1—N3^i	2.5558 (16)	C7—C7^i	1.529 (4)
Tb1—N3	2.5558 (16)	C7—H7A	0.9900
Tb1—N1	2.891 (2)	C7—H7B	0.9900
O1—C10	1.324 (2)	C8—C9	1.503 (3)
O2—N1	1.266 (2)	C8—H8A	0.9900
O3—N1	1.220 (3)	C8—H8B	0.9900
N1—O2^i	1.266 (2)	C9—C14	1.393 (3)
N2—C1	1.342 (3)	C9—C10	1.412 (3)
N2—C5	1.347 (3)	C10—C11	1.409 (3)
N3—C6	1.485 (2)	C11—C12	1.390 (3)
N3—C7	1.489 (2)	C11—H11	0.9500
N3—C8	1.498 (2)	C12—C13	1.391 (3)
C1—C2	1.391 (3)	C12—H12	0.9500
C1—H1	0.9500	C13—C14	1.392 (3)
C2—C3	1.380 (3)	C13—H13	0.9500
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.388 (3)
O1^i—Tb1—O1	154.07 (7)	C8—N3—Tb1	111.56 (11)
O1^i—Tb1—O2^i	128.52 (6)	N2—C1—C2	123.4 (2)
O1—Tb1—O2^i	77.36 (6)	N2—C1—H1	118.3
O1^i—Tb1—O2	77.36 (6)	C2—C1—H1	118.3
O1—Tb1—O2	128.52 (6)	C3—C2—C1	118.3 (2)
O2^i—Tb1—O2	51.64 (9)	C3—C2—H2	120.9
O1^i—Tb1—N2^i	98.20 (5)	C1—C2—H2	120.9
O1—Tb1—N2^i	86.89 (5)	C2—C3—C4	119.11 (19)
O2^i—Tb1—N2^i	80.45 (6)	C2—C3—H3	120.4
O2—Tb1—N2^i	79.10 (6)	C4—C3—H3	120.4
O1^i—Tb1—N2	86.89 (5)	C3—C4—C5	119.2 (2)
O1—Tb1—N2	98.20 (5)	C3—C4—H4	120.4
O2^i—Tb1—N2	79.10 (6)	C5—C4—H4	120.4
O2—Tb1—N2	80.45 (6)	N2—C5—C4	122.21 (19)
N2^i—Tb1—N2	157.26 (8)	N2—C5—C6	117.05 (16)
O1^i—Tb1—N3^i	76.70 (5)	C4—C5—C6	120.74 (19)
O1—Tb1—N3^i	82.18 (5)	N3—C6—C5	111.54 (16)
O2^i—Tb1—N3^i	141.99 (5)	N3—C6—H6A	109.3
O2—Tb1—N3^i	132.91 (6)	C5—C6—H6A	109.3
N2^i—Tb1—N3^i	66.65 (5)	N3—C6—H6B	109.3
N2—Tb1—N3^i	135.88 (5)	C5—C6—H6B	109.3
O1^i—Tb1—N3	82.18 (5)	H6A—C6—H6B	108.0
O1—Tb1—N3	76.70 (5)	N3—C7—C7^i	113.05 (13)
O2^i—Tb1—N3	132.91 (6)	N3—C7—H7A	109.0
O2—Tb1—N3	141.99 (5)	C7^i—C7—H7A	109.0
N2^i—Tb1—N3	135.88 (5)	N3—C7—H7B	109.0
N2—Tb1—N3	66.65 (5)	C7^i—C7—H7B	109.0
N3^i—Tb1—N3	70.67 (7)	H7A—C7—H7B	107.8
O1^i—Tb1—N1	102.97 (4)	N3—C8—C9	116.63 (16)
O1—Tb1—N1	102.97 (4)	N3—C8—H8A	108.1
O2^i—Tb1—N1	25.82 (4)	C9—C8—H8A	108.1
O2—Tb1—N1	25.82 (4)	N3—C8—H8B	108.1
N2^i—Tb1—N1	78.63 (4)	C9—C8—H8B	108.1
N2—Tb1—N1	78.63 (4)	H8A—C8—H8B	107.3
N3^i—Tb1—N1	144.67 (4)	C14—C9—C10	120.42 (18)
N3—Tb1—N1	144.67 (4)	C14—C9—C8	120.25 (19)
C10—O1—Tb1	139.80 (12)	C10—C9—C8	119.08 (19)
N1—O2—Tb1	95.73 (12)	O1—C10—C11	121.83 (18)
O3—N1—O2	121.55 (11)	O1—C10—C9	120.05 (17)
O3—N1—O2^i	121.55 (11)	C11—C10—C9	118.13 (18)
O2—N1—O2^i	116.9 (2)	C12—C11—C10	120.67 (19)
O3—N1—Tb1	180.0	C12—C11—H11	119.7
O2—N1—Tb1	58.45 (11)	C10—C11—H11	119.7
O2^i—N1—Tb1	58.45 (11)	C11—C12—C13	120.8 (2)
C1—N2—C5	117.83 (17)	C11—C12—H12	119.6
C1—N2—Tb1	126.43 (14)	C13—C12—H12	119.6
C5—N2—Tb1	115.74 (12)	C12—C13—C14	119.2 (2)
C6—N3—C7	109.19 (15)	C12—C13—H13	120.4
C6—N3—C8	107.09 (15)	C14—C13—H13	120.4
C7—N3—C8	111.34 (15)	C13—C14—C9	120.8 (2)
C6—N3—Tb1	105.69 (12)	C13—C14—H14	119.6
C7—N3—Tb1	111.67 (11)	C9—C14—H14	119.6
Tb1—O2—N1—O3	180.000 (1)	Tb1—N3—C7—C7^i	−38.2 (2)
Tb1—O2—N1—O2^i	0.000 (1)	C6—N3—C8—C9	−179.19 (19)
C5—N2—C1—C2	−0.5 (3)	C7—N3—C8—C9	−59.9 (2)
Tb1—N2—C1—C2	178.82 (17)	Tb1—N3—C8—C9	65.61 (19)
N2—C1—C2—C3	0.2 (4)	N3—C8—C9—C14	125.3 (2)
C1—C2—C3—C4	0.8 (3)	N3—C8—C9—C10	−60.3 (3)
C2—C3—C4—C5	−1.3 (3)	Tb1—O1—C10—C11	−142.18 (16)
C1—N2—C5—C4	0.0 (3)	Tb1—O1—C10—C9	37.5 (3)
Tb1—N2—C5—C4	−179.43 (14)	C14—C9—C10—O1	−179.29 (18)
C1—N2—C5—C6	−179.33 (18)	C8—C9—C10—O1	6.3 (3)
Tb1—N2—C5—C6	1.2 (2)	C14—C9—C10—C11	0.4 (3)
C3—C4—C5—N2	0.9 (3)	C8—C9—C10—C11	−174.00 (18)
C3—C4—C5—C6	−179.80 (18)	O1—C10—C11—C12	179.21 (19)
C7—N3—C6—C5	173.14 (16)	C9—C10—C11—C12	−0.5 (3)
C8—N3—C6—C5	−66.2 (2)	C10—C11—C12—C13	0.3 (3)
Tb1—N3—C6—C5	52.88 (17)	C11—C12—C13—C14	−0.2 (4)
N2—C5—C6—N3	−38.3 (2)	C12—C13—C14—C9	0.1 (3)
C4—C5—C6—N3	142.41 (18)	C10—C9—C14—C13	−0.2 (3)
C6—N3—C7—C7^i	−154.7 (2)	C8—C9—C14—C13	174.1 (2)
C8—N3—C7—C7^i	87.2 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O3^ii	0.99	2.37	3.338 (3)	166

Symmetry code: (ii) x+1/2, y+1/2, z.