Di-μ-acetato-bis­[triaqua­bis(thio­cyanato-κN)(pyridine N-oxide-κO)neodymium(III)]

The title binuclear complex, [Nd₂(μ-C₂H₃O₂)₂(NCS)₄(C₅H₅NO)₂(H₂O)₆], lies about an inversion centre at the centroid of the four-membered Nd₂O₂ ring, with the two acetate ions acting as bridging ligands. A monodentate pyridine N-oxide ligand, two terminal thio­cyanate groups and three water mol­ecules complete the coordination environments of each nine-coordinate Nd^III atom. O—H...O, O—H...N and O—H...S hydrogen bonds link the mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.031
• wR factor = 0.071
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Nd1    -   O3      ..       5.76 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Nd1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  N1      ..       2.70 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         57
            ND1 -N2  -C9  -S2      3.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         66
            ND1 -N3  -C8  -S1    -75.00  8.00   1.555   1.555   1.555   1.555

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Nd1         (2)       1.57
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Acetate, thiocyanate and pyridine N-oxide or its derivatives are all known to function as bridging ligands (Kato et al., 1964; Zhang et al., 2006), and we are interested in complexes with mixed bridge ligands which led to the synthesis of the title complex (I) and we report its structure here, Fig. 1. In the binuclear structure acetate acts as a bridging ligand, whereas thiocyanate, water and pyridine N-oxide only function as terminal ligands. The Nd and bridging acetate O atoms form a four-membered ring by virtue of the crystallographic inversion center which is at the centroid of the ring. The distance between the bridged Nd(III) ions is 4.4167 (7) Å, and atoms Nd1, Nd1ⁱ, O3 and O3ⁱ are strictly coplanar (i = -x + 2, -y + 2, -z + 1). An extensive set of O—H···O, O—H···N and O—H···S hydrogen bonds (Table 1) connect the binuclear units into a three-dimensional supermolecular structure.

Related literature

For related structures, see: Kato et al. (1964); Zhang et al. (2006).

S2. Experimental

Nd(ClO₄)₃.6H₂O (0.2891 g, 0.525 mmol), NaSCN (0.0872 g, 1.08 mmol), pyridine N-oxide (0.0502 g, 0.528 mmol) and Na(CH₃COO) (0.0435 g, 0.530 mmol) were each dissolved in 5 ml of water. The solutions were then mixed together and stirred for a few minutes. Colourless transparent single crystals were obtained on allowing the solution to stand for two weeks at room temperature.

S3. Refinement

The H atoms from H₂O were found in a difference Fourier map and fixed with d(O—H) = 0.8200–0.8502 Å, U_iso(H) = 1.5_eq(O). Other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, U_iso(H) = 1.2_eq(C) for the pyridine ring; C—H = 0.96 Å, U_iso(H) = 1.5_eq(C) for the methyl groups.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Binuclear structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x + 2, -y + 2, -z + 1].

Di-µ-acetato-bis[triaquabis(thiocyanato-κN)(pyridine N-oxide-κO)neodymium(III)]

Crystal data

[Nd2(C2H3O2)2(NCS)4(C5H5NO)2(H2O)6]	F(000) = 916
Mr = 937.18	Dx = 1.891 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3146 reflections
a = 9.1588 (15) Å	θ = 2.2–26.8°
b = 16.185 (3) Å	µ = 3.43 mm^−1
c = 11.3892 (18) Å	T = 298 K
β = 102.813 (2)°	Prism, colourless
V = 1646.3 (5) Å^3	0.56 × 0.07 × 0.06 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2900 independent reflections
Radiation source: fine-focus sealed tube	2545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.249, Tmax = 0.821	k = −19→17
6827 measured reflections	l = −13→13

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0303P)^2 + 1.869P] where P = (Fo^2 + 2Fc^2)/3
2900 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 1.39 e Å^−3
9 restraints	Δρmin = −0.95 e Å^−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
Nd1	0.81351 (3)	0.914089 (14)	0.50289 (2)	0.02859 (10)
S2	0.9773 (2)	0.60651 (9)	0.60836 (14)	0.0636 (5)
S1	0.4319 (2)	0.85963 (10)	0.77853 (17)	0.0731 (5)
C6	0.8144 (5)	1.0972 (3)	0.5558 (4)	0.0324 (11)
O3	0.9353 (3)	1.07210 (19)	0.5326 (3)	0.0367 (8)
N1	0.9405 (4)	0.9164 (2)	0.8172 (3)	0.0355 (9)
O6	0.5523 (4)	0.9109 (2)	0.3919 (3)	0.0516 (10)
H9	0.4761	0.9210	0.4205	0.077*
H8	0.5265	0.9077	0.3156	0.077*
O1	0.9538 (4)	0.9411 (2)	0.7079 (3)	0.0465 (9)
O2	0.7084 (3)	1.0477 (2)	0.5525 (3)	0.0384 (8)
O5	0.7805 (5)	0.8141 (2)	0.3268 (3)	0.0626 (11)
H10	0.7260	0.8323	0.2620	0.094*
H11	0.8307	0.7728	0.3133	0.094*
N3	0.6407 (5)	0.8676 (3)	0.6364 (4)	0.0471 (11)
N2	0.9058 (6)	0.7726 (3)	0.5737 (5)	0.0645 (14)
C9	0.9357 (6)	0.7034 (4)	0.5892 (4)	0.0447 (13)
C2	1.0314 (6)	0.8571 (3)	0.8735 (5)	0.0514 (14)
H2	1.0996	0.8315	0.8358	0.062*
C7	0.7971 (7)	1.1846 (4)	0.5870 (7)	0.076 (2)
H7A	0.6963	1.1942	0.5948	0.114*
H7B	0.8186	1.2194	0.5246	0.114*
H7C	0.8653	1.1972	0.6618	0.114*
C1	1.0225 (7)	0.8348 (4)	0.9877 (6)	0.0655 (18)
H1	1.0855	0.7939	1.0281	0.079*
O4	0.7882 (4)	0.9858 (2)	0.3048 (3)	0.0408 (8)
H7	0.7158	1.0170	0.2940	0.061*
H6	0.8692	1.0094	0.2993	0.061*
C3	0.8400 (6)	0.9531 (3)	0.8683 (5)	0.0438 (12)
H3	0.7771	0.9936	0.8268	0.053*
C4	0.8298 (7)	0.9311 (4)	0.9810 (5)	0.0622 (18)
H4	0.7595	0.9565	1.0167	0.075*
C5	0.9224 (8)	0.8719 (5)	1.0422 (6)	0.077 (2)
H5	0.9169	0.8571	1.1200	0.092*
C8	0.5514 (5)	0.8627 (3)	0.6923 (4)	0.0358 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.02128 (15)	0.03128 (15)	0.03543 (16)	0.00006 (10)	0.01103 (11)	0.00093 (11)
S2	0.0951 (13)	0.0463 (9)	0.0496 (9)	0.0206 (8)	0.0162 (9)	0.0095 (7)
S1	0.0744 (12)	0.0619 (10)	0.1033 (13)	0.0212 (8)	0.0629 (11)	0.0405 (10)
C6	0.023 (3)	0.032 (3)	0.044 (3)	0.0065 (19)	0.012 (2)	−0.003 (2)
O3	0.0235 (17)	0.0415 (19)	0.048 (2)	0.0027 (14)	0.0133 (15)	0.0014 (15)
N1	0.030 (2)	0.041 (2)	0.035 (2)	−0.0081 (18)	0.0058 (18)	0.0038 (18)
O6	0.0186 (17)	0.090 (3)	0.048 (2)	−0.0006 (17)	0.0123 (16)	−0.013 (2)
O1	0.037 (2)	0.070 (2)	0.0341 (18)	−0.0149 (18)	0.0091 (16)	0.0106 (17)
O2	0.0251 (18)	0.0377 (19)	0.057 (2)	−0.0008 (15)	0.0186 (16)	−0.0071 (16)
O5	0.072 (3)	0.051 (2)	0.059 (2)	0.020 (2)	0.002 (2)	−0.015 (2)
N3	0.041 (3)	0.054 (3)	0.049 (3)	−0.005 (2)	0.015 (2)	0.008 (2)
N2	0.075 (4)	0.051 (3)	0.072 (3)	0.018 (3)	0.026 (3)	0.020 (3)
C9	0.043 (3)	0.055 (4)	0.037 (3)	0.007 (3)	0.009 (2)	0.009 (3)
C2	0.045 (3)	0.049 (3)	0.061 (4)	0.007 (3)	0.013 (3)	0.007 (3)
C7	0.049 (4)	0.043 (4)	0.144 (7)	−0.008 (3)	0.036 (4)	−0.025 (4)
C1	0.062 (4)	0.064 (4)	0.063 (4)	−0.005 (3)	−0.003 (3)	0.026 (3)
O4	0.0265 (18)	0.048 (2)	0.048 (2)	−0.0047 (15)	0.0069 (15)	0.0086 (16)
C3	0.033 (3)	0.049 (3)	0.050 (3)	−0.001 (2)	0.010 (2)	−0.004 (3)
C4	0.052 (4)	0.092 (5)	0.049 (4)	−0.014 (3)	0.025 (3)	−0.013 (3)
C5	0.075 (5)	0.110 (6)	0.046 (4)	−0.032 (5)	0.017 (4)	0.016 (4)
C8	0.035 (3)	0.037 (3)	0.036 (3)	−0.002 (2)	0.010 (2)	0.007 (2)

Geometric parameters (Å, º)

Nd1—O3^i	2.433 (3)	O6—H8	0.8502
Nd1—O1	2.441 (3)	O5—H10	0.8473
Nd1—O6	2.446 (3)	O5—H11	0.8439
Nd1—O2	2.483 (3)	N3—C8	1.145 (6)
Nd1—O4	2.502 (3)	N2—C9	1.157 (7)
Nd1—N2	2.511 (5)	C2—C1	1.369 (8)
Nd1—N3	2.540 (4)	C2—H2	0.9300
Nd1—O5	2.542 (4)	C7—H7A	0.9600
Nd1—O3	2.781 (3)	C7—H7B	0.9600
S2—C9	1.617 (6)	C7—H7C	0.9600
S1—C8	1.626 (5)	C1—C5	1.357 (10)
C6—O2	1.253 (5)	C1—H1	0.9300
C6—O3	1.261 (5)	O4—H7	0.8200
C6—C7	1.476 (7)	O4—H6	0.8492
O3—Nd1^i	2.433 (3)	C3—C4	1.354 (8)
N1—C3	1.333 (6)	C3—H3	0.9300
N1—C2	1.338 (6)	C4—C5	1.365 (10)
N1—O1	1.339 (5)	C4—H4	0.9300
O6—H9	0.8483	C5—H5	0.9300
O3^i—Nd1—O1	79.97 (11)	Nd1^i—O3—Nd1	115.65 (11)
O3^i—Nd1—O6	140.26 (11)	C3—N1—C2	121.8 (5)
O1—Nd1—O6	138.13 (12)	C3—N1—O1	119.2 (4)
O3^i—Nd1—O2	112.74 (10)	C2—N1—O1	119.0 (4)
O1—Nd1—O2	76.98 (12)	Nd1—O6—H9	126.2
O6—Nd1—O2	75.61 (11)	Nd1—O6—H8	123.2
O3^i—Nd1—O4	73.13 (10)	H9—O6—H8	109.8
O1—Nd1—O4	134.66 (11)	N1—O1—Nd1	134.3 (3)
O6—Nd1—O4	70.08 (11)	C6—O2—Nd1	103.1 (3)
O2—Nd1—O4	80.67 (11)	Nd1—O5—H10	114.2
O3^i—Nd1—N2	82.75 (14)	Nd1—O5—H11	132.3
O1—Nd1—N2	77.77 (15)	H10—O5—H11	110.8
O6—Nd1—N2	111.58 (16)	C8—N3—Nd1	165.9 (4)
O2—Nd1—N2	147.25 (14)	C9—N2—Nd1	169.4 (5)
O4—Nd1—N2	132.08 (14)	N2—C9—S2	179.0 (5)
O3^i—Nd1—N3	149.81 (12)	N1—C2—C1	118.9 (6)
O1—Nd1—N3	75.30 (12)	N1—C2—H2	120.5
O6—Nd1—N3	68.60 (13)	C1—C2—H2	120.5
O2—Nd1—N3	78.31 (13)	C6—C7—H7A	109.5
O4—Nd1—N3	137.05 (12)	C6—C7—H7B	109.5
N2—Nd1—N3	75.37 (16)	H7A—C7—H7B	109.5
O3^i—Nd1—O5	83.04 (12)	C6—C7—H7C	109.5
O1—Nd1—O5	144.44 (13)	H7A—C7—H7C	109.5
O6—Nd1—O5	69.37 (12)	H7B—C7—H7C	109.5
O2—Nd1—O5	138.57 (12)	C5—C1—C2	120.5 (6)
O4—Nd1—O5	67.24 (12)	C5—C1—H1	119.8
N2—Nd1—O5	69.24 (15)	C2—C1—H1	119.8
N3—Nd1—O5	107.62 (14)	Nd1—O4—H7	109.4
O3^i—Nd1—O3	64.35 (12)	Nd1—O4—H6	111.6
O1—Nd1—O3	66.88 (11)	H7—O4—H6	113.8
O6—Nd1—O3	113.70 (11)	N1—C3—C4	119.8 (6)
O2—Nd1—O3	48.43 (10)	N1—C3—H3	120.1
O4—Nd1—O3	68.72 (10)	C4—C3—H3	120.1
N2—Nd1—O3	134.63 (15)	C3—C4—C5	120.2 (6)
N3—Nd1—O3	119.09 (12)	C3—C4—H4	119.9
O5—Nd1—O3	130.97 (12)	C5—C4—H4	119.9
O2—C6—O3	119.9 (4)	C1—C5—C4	118.9 (6)
O2—C6—C7	119.8 (4)	C1—C5—H5	120.6
O3—C6—C7	120.3 (4)	C4—C5—H5	120.6
C6—O3—Nd1^i	155.7 (3)	N3—C8—S1	176.2 (5)
C6—O3—Nd1	88.6 (3)
O2—C6—O3—Nd1^i	174.7 (5)	O1—Nd1—O2—C6	69.5 (3)
C7—C6—O3—Nd1^i	−5.3 (11)	O6—Nd1—O2—C6	−142.5 (3)
O2—C6—O3—Nd1	−1.7 (4)	O4—Nd1—O2—C6	−70.8 (3)
C7—C6—O3—Nd1	178.4 (5)	N2—Nd1—O2—C6	109.9 (4)
O3^i—Nd1—O3—C6	178.3 (3)	N3—Nd1—O2—C6	146.9 (3)
O1—Nd1—O3—C6	−92.0 (3)	O5—Nd1—O2—C6	−109.6 (3)
O6—Nd1—O3—C6	42.2 (3)	O3—Nd1—O2—C6	−1.0 (3)
O2—Nd1—O3—C6	1.0 (3)	O3^i—Nd1—N3—C8	129.8 (16)
O4—Nd1—O3—C6	97.5 (3)	O1—Nd1—N3—C8	93.8 (16)
N2—Nd1—O3—C6	−133.8 (3)	O6—Nd1—N3—C8	−64.6 (16)
N3—Nd1—O3—C6	−35.6 (3)	O2—Nd1—N3—C8	14.4 (16)
O5—Nd1—O3—C6	124.8 (3)	O4—Nd1—N3—C8	−47.9 (17)
O3^i—Nd1—O3—Nd1^i	0.0	N2—Nd1—N3—C8	174.7 (17)
O1—Nd1—O3—Nd1^i	89.71 (15)	O5—Nd1—N3—C8	−123.1 (16)
O6—Nd1—O3—Nd1^i	−136.12 (13)	O3—Nd1—N3—C8	41.5 (17)
O2—Nd1—O3—Nd1^i	−177.4 (2)	O3^i—Nd1—N2—C9	−102 (3)
O4—Nd1—O3—Nd1^i	−80.88 (14)	O1—Nd1—N2—C9	177 (3)
N2—Nd1—O3—Nd1^i	47.9 (2)	O6—Nd1—N2—C9	40 (3)
N3—Nd1—O3—Nd1^i	146.10 (14)	O2—Nd1—N2—C9	137 (3)
O5—Nd1—O3—Nd1^i	−53.50 (19)	O4—Nd1—N2—C9	−42 (3)
C3—N1—O1—Nd1	−79.8 (5)	N3—Nd1—N2—C9	99 (3)
C2—N1—O1—Nd1	102.1 (5)	O5—Nd1—N2—C9	−17 (3)
O3^i—Nd1—O1—N1	−146.6 (4)	O3—Nd1—N2—C9	−144 (3)
O6—Nd1—O1—N1	46.9 (5)	Nd1—N2—C9—S2	30 (34)
O2—Nd1—O1—N1	97.1 (4)	C3—N1—C2—C1	−1.2 (8)
O4—Nd1—O1—N1	159.5 (4)	O1—N1—C2—C1	176.9 (5)
N2—Nd1—O1—N1	−61.9 (4)	N1—C2—C1—C5	0.4 (9)
N3—Nd1—O1—N1	16.0 (4)	C2—N1—C3—C4	0.9 (8)
O5—Nd1—O1—N1	−83.9 (5)	O1—N1—C3—C4	−177.2 (5)
O3—Nd1—O1—N1	147.2 (4)	N1—C3—C4—C5	0.2 (9)
O3—C6—O2—Nd1	1.9 (5)	C2—C1—C5—C4	0.7 (10)
C7—C6—O2—Nd1	−178.1 (5)	C3—C4—C5—C1	−1.0 (10)
O3^i—Nd1—O2—C6	−3.6 (3)	Nd1—N3—C8—S1	−75 (8)

Symmetry code: (i) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H6···O1^i	0.85	1.83	2.675 (5)	178
O6—H9···O2^ii	0.85	1.85	2.686 (4)	167
O6—H8···S2^iii	0.85	2.31	3.162 (4)	175
O5—H10···S2^iii	0.85	2.73	3.534 (4)	159
O5—H11···S1^iv	0.84	2.40	3.236 (4)	169
O4—H7···S1^ii	0.82	2.45	3.220 (4)	157
O4—H6···N1^i	0.85	2.70	3.484 (5)	155

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−1/2.