Hexa­aqua­bis­(di­cyano­guanidine)­terbium(III) trichloride

In the title compound, [Tb(C₂H₄N₄)₂(H₂O)₆]Cl₃, the coord­ination of the terbium(III) ion is a square-antiprismatic arrangement by six O atoms and two monodentate cyano­guanidine (cnge) mol­ecules forming covalent Tb-N bonds of 2.446 (4) Å through their nitrile N atoms. The crystal structure consists of metal ion layers separated by the organic mol­ecules along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-C) = 0.007 Å
• R factor = 0.022
• wR factor = 0.055
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         Tb
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor ....       2.10
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H42    ...          ?
PLAT731_ALERT_1_C Bond    Calc     0.82(5), Rep     0.82(2) ......       2.50 su-Rat
              O1   -H12     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(6), Rep     0.82(2) ......       3.00 su-Rat
              O2   -H22     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(5), Rep     0.81(2) ......       2.50 su-Rat
              O3   -H31     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(5), Rep     0.81(2) ......       2.50 su-Rat
              O3   -H32     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(6), Rep     0.85(2) ......       3.00 su-Rat
              N4   -H42     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(5), Rep     0.82(2) ......       2.50 su-Rat
              O1   -H12     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(6), Rep     0.82(2) ......       3.00 su-Rat
              O2   -H22     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(5), Rep     0.81(2) ......       2.50 su-Rat
              O3   -H31     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(5), Rep     0.81(2) ......       2.50 su-Rat
              O3   -H32     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(6), Rep     0.85(2) ......       3.00 su-Rat
              N4   -H42     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.31(6), Rep     2.31(2) ......       3.00 su-Rat
              H31  -CL1     1.555   8.544
PLAT736_ALERT_1_C H...A   Calc     2.23(5), Rep     2.23(2) ......       2.50 su-Rat
              H32  -CL1     1.555   1.555

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           28.29
           From the CIF: _reflns_number_total               2185
           Count of symmetry unique reflns         1203
           Completeness (_total/calc)            181.63%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       982
           Fraction of Friedel pairs measured     0.816
           Are heavy atom types Z>Si present          yes

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

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

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Hexaaquabis(dicyanoguanidine)terbium(III) trichloride

Crystal data

[Tb(C2H4N4)2(H2O)6]·Cl3	F(000) = 2112
Mr = 541.55	Dx = 1.928 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 6486 reflections
a = 29.425 (5) Å	θ = 2.7–28.3°
b = 9.2613 (14) Å	µ = 4.26 mm^−1
c = 13.690 (2) Å	T = 293 K
V = 3730.6 (10) Å^3	Prism, colourless
Z = 8	0.31 × 0.08 × 0.05 mm

Data collection

Bruker AXS APEX CCD diffractometer	2185 independent reflections
Radiation source: fine-focus sealed tube	2065 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 28.3°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −39→39
Tmin = 0.290, Tmax = 0.808	k = −12→8
6486 measured reflections	l = −18→17

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0315P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.055	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.43 e Å^−3
2185 reflections	Δρmin = −0.60 e Å^−3
142 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
11 restraints	Extinction coefficient: 0.00174 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.030 (13)

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.

PLAT731 Type_1 Test for consistency of Bond su's and Coordinate su's in CIF A large ratio of the reported and calculated bond s.u.'s is found. The use of a DFIX instruction might cause such a warning since calculated s.u.'s are based on reported variances only. Note_1: su's on the unitcell dimensions are taken into account in the calculation of expected su's. This may result in large differences between expected and reported su's when this contribution is not included in the reported su's, in particular for inaccurate unitcells. Note_2: Another source for the discrepancy between calculated and reported su's can be that the validation software has access only to the variances of the refined parameters as opposed to the full co-variance matrix used by e.g. SHELXL for the calculation of derived parameters with associated su's. Constrained/restrained refinement may cause largei co-variances.

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
Tb	0.0000	0.0000	0.10089 (3)	0.01999 (9)
Cl1	0.16603 (4)	−0.02478 (13)	0.12593 (7)	0.0356 (2)
Cl2	0.0000	0.5000	0.1976 (2)	0.0492 (5)
O1	0.04611 (10)	0.1990 (3)	0.1609 (2)	0.0318 (6)
H11	0.0568 (18)	0.199 (7)	0.216 (2)	0.048 (16)*
H12	0.032 (2)	0.275 (5)	0.155 (6)	0.07 (2)*
O2	0.00361 (10)	0.1841 (5)	−0.0176 (3)	0.0485 (11)
H21	0.0287 (11)	0.214 (6)	−0.033 (4)	0.042 (16)*
H22	−0.016 (2)	0.200 (9)	−0.059 (5)	0.07 (2)*
O3	0.07309 (11)	−0.0297 (4)	0.0302 (3)	0.0350 (7)
H31	0.079 (2)	−0.092 (6)	−0.010 (4)	0.059 (18)*
H32	0.0965 (15)	−0.026 (7)	0.062 (5)	0.06 (2)*
C1	0.06201 (13)	−0.1393 (5)	0.3052 (3)	0.0287 (8)
C2	0.12159 (13)	−0.1881 (4)	0.4076 (3)	0.0285 (8)
N1	0.04525 (11)	−0.1007 (4)	0.2344 (3)	0.0354 (8)
N2	0.07682 (12)	−0.1836 (5)	0.3896 (3)	0.0358 (8)
N3	0.15310 (12)	−0.1520 (5)	0.3449 (3)	0.0439 (10)
H33	0.1797 (9)	−0.156 (5)	0.369 (4)	0.039 (14)*
H34	0.1485 (19)	−0.120 (6)	0.287 (2)	0.050 (16)*
N4	0.13413 (16)	−0.2305 (5)	0.4966 (4)	0.0440 (11)
H41	0.1621 (10)	−0.254 (6)	0.507 (7)	0.06 (2)*
H42	0.116 (2)	−0.232 (6)	0.545 (4)	0.05 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb	0.01711 (11)	0.02478 (12)	0.01808 (12)	−0.00021 (10)	0.000	0.000
Cl1	0.0266 (5)	0.0518 (6)	0.0284 (6)	−0.0048 (4)	−0.0025 (3)	−0.0053 (5)
Cl2	0.0298 (8)	0.0351 (9)	0.0825 (16)	0.0034 (6)	0.000	0.000
O1	0.0363 (16)	0.0269 (15)	0.0322 (16)	−0.0005 (12)	−0.0099 (13)	−0.0014 (13)
O2	0.0232 (16)	0.073 (3)	0.050 (2)	−0.0123 (16)	−0.0092 (14)	0.037 (2)
O3	0.0196 (14)	0.0504 (19)	0.0352 (18)	0.0024 (13)	0.0000 (12)	−0.0114 (15)
C1	0.0239 (18)	0.031 (2)	0.031 (2)	−0.0048 (15)	0.0011 (15)	0.0074 (16)
C2	0.0295 (19)	0.0258 (18)	0.0301 (19)	−0.0023 (15)	−0.0072 (15)	0.0067 (16)
N1	0.0309 (17)	0.040 (2)	0.0353 (19)	−0.0024 (15)	−0.0085 (15)	0.0104 (16)
N2	0.0291 (18)	0.046 (2)	0.033 (2)	−0.0032 (15)	−0.0023 (14)	0.0156 (18)
N3	0.0256 (17)	0.064 (3)	0.042 (2)	−0.0072 (17)	−0.0039 (17)	0.018 (2)
N4	0.035 (2)	0.055 (3)	0.042 (3)	0.0040 (18)	−0.0104 (19)	0.0144 (19)

Geometric parameters (Å, º)

Tb—O1	2.432 (3)	O3—H31	0.81 (2)
Tb—O1^i	2.432 (3)	O3—H32	0.81 (2)
Tb—O2	2.356 (4)	C1—N1	1.145 (5)
Tb—O2^i	2.356 (4)	C1—N2	1.301 (5)
Tb—O3	2.374 (3)	C2—N2	1.341 (5)
Tb—O3^i	2.374 (3)	C2—N3	1.307 (5)
Tb—N1	2.446 (4)	C2—N4	1.332 (6)
Tb—N1^i	2.446 (4)	N3—H33	0.853 (19)
O1—H11	0.82 (2)	N3—H34	0.86 (2)
O1—H12	0.82 (2)	N4—H41	0.86 (2)
O2—H21	0.82 (2)	N4—H42	0.85 (2)
O2—H22	0.82 (2)
O2^i—Tb—O2	93.0 (3)	O1—Tb—N1^i	76.24 (11)
O2^i—Tb—O3^i	76.25 (13)	O1^i—Tb—N1^i	74.50 (11)
O2—Tb—O3^i	71.12 (11)	N1—Tb—N1^i	83.32 (19)
O2^i—Tb—O3	71.12 (11)	Tb—O1—H11	122 (4)
O2—Tb—O3	76.25 (13)	Tb—O1—H12	110 (6)
O3^i—Tb—O3	131.88 (17)	H11—O1—H12	107 (7)
O2^i—Tb—O1	143.75 (11)	Tb—O2—H21	118 (4)
O2—Tb—O1	70.06 (13)	Tb—O2—H22	125 (6)
O3^i—Tb—O1	123.74 (12)	H21—O2—H22	113 (8)
O3—Tb—O1	73.75 (12)	Tb—O3—H31	123 (4)
O2^i—Tb—O1^i	70.06 (13)	Tb—O3—H32	123 (5)
O2—Tb—O1^i	143.75 (12)	H31—O3—H32	102 (6)
O3^i—Tb—O1^i	73.75 (12)	N1—C1—N2	174.0 (4)
O3—Tb—O1^i	123.74 (12)	N3—C2—N4	118.7 (4)
O1—Tb—O1^i	140.49 (16)	N3—C2—N2	124.6 (4)
O2^i—Tb—N1	105.24 (16)	N4—C2—N2	116.7 (4)
O2—Tb—N1	139.99 (12)	C1—N1—Tb	170.5 (4)
O3^i—Tb—N1	147.33 (12)	C1—N2—C2	120.2 (4)
O3—Tb—N1	76.55 (13)	C2—N3—H33	113 (4)
O1—Tb—N1	74.50 (11)	C2—N3—H34	126 (4)
O1^i—Tb—N1	76.24 (11)	H33—N3—H34	121 (5)
O2^i—Tb—N1^i	139.99 (12)	C2—N4—H41	119 (6)
O2—Tb—N1^i	105.24 (16)	C2—N4—H42	123 (5)
O3^i—Tb—N1^i	76.55 (13)	H41—N4—H42	117 (8)
O3—Tb—N1^i	147.33 (12)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···Cl1^ii	0.82 (2)	2.34 (2)	3.156 (3)	174 (6)
O1—H12···Cl2	0.82 (2)	2.36 (3)	3.141 (3)	159 (8)
O2—H21···N2^iii	0.82 (2)	2.00 (3)	2.785 (5)	160 (6)
O2—H22···Cl1^iv	0.82 (2)	2.29 (4)	3.077 (3)	159 (8)
O3—H31···Cl1^v	0.81 (2)	2.31 (2)	3.117 (4)	172 (6)
O3—H32···Cl1	0.81 (2)	2.23 (2)	3.033 (3)	171 (7)
N3—H33···Cl2^vi	0.85 (2)	2.49 (2)	3.306 (4)	161 (4)
N3—H34···Cl1	0.86 (2)	2.43 (3)	3.243 (5)	159 (5)
N4—H41···Cl2^vi	0.86 (2)	2.71 (5)	3.480 (5)	149 (7)
N4—H42···O1^vii	0.85 (2)	2.67 (3)	3.492 (6)	161 (6)

Symmetry codes: (ii) −x+1/4, y+1/4, z+1/4; (iii) x, y+1/2, z−1/2; (iv) x−1/4, −y+1/4, z−1/4; (v) −x+1/4, y−1/4, z−1/4; (vi) x+1/4, −y+1/4, z+1/4; (vii) x, y−1/2, z+1/2.