Crystal structure of poly[(2,2′-bi­pyridine-κ2N,N′)tetra-μ2-cyanido-κ4C:N;κ4N:C-manganese(II)disilver(I)]

Theppitak, C.; Chainok, K.

doi:10.1107/S205698901501676X

metal-organic compounds

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Volume 71| Part 10| October 2015| Pages m179-m180

doi:10.1107/S205698901501676X

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Crystal structure of poly[(2,2′-bipyridine-κ²N,N′)tetra-μ₂-cyanido-κ⁴C:N;κ⁴N:C-manganese(II)disilver(I)]

Chatphorn Theppitak ^a and Kittipong Chainok ^b ^*

^aDepartment of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok, 65000, Thailand, and ^bDepartment of Physics, Faculty of Science and Technology, Thammasat University, Khlong Luang, Pathum Thani, 12120, Thailand
^*Correspondence e-mail: kc@tu.ac.th

Edited by A. Van der Lee, Université de Montpellier II, France (Received 4 September 2015; accepted 8 September 2015; online 12 September 2015)

The title compound, [Ag₂Mn(CN)₄(C₁₀H₈N₂)]_n or Mn(bipy){Ag(CN)₂}₂ (bipy = 2,2′-bipyridine) is isostructural with Cd(bipy){Au(CN)₂}₂ [Guo et al. (2009 ). CrystEngComm, 11, 61–66]. The Mn^II atom has crystallographically imposed twofold symmetry and a distorted octahedral coordination sphere consisting of six N atoms from one bipyridine ligand and four dicyanoargentate(I) anions, [Ag(CN)₂]⁻, while the Ag^I atom of the complex anion displays the expected linear geometry. Each [Ag(CN)₂]⁻ unit connects to two neighbouring [Mn(bipy)]²⁺ cations to give an threefold interpenetrating quartz-like three-dimensional framework. No directional interactions beyond van der Waals contacts are observed.

Keywords: crystal structure; dicyanoargentate(I); manganese(II); triple interpenetration.

CCDC reference: 1422937

1. Related literature

For related crystal structures, see: Soma et al. (1994 ); Guo et al. (2009). For the use of [Ag(CN)₂]⁻ as a building block for the construction of cyanide-bridged silver(I)–iron(II) spin-crossover coordination polymers, see: Shorrock et al. (2002 ); Galet et al. (2003 ); Niel et al. (2003 ); Muñoz et al. (2007 ).

2. Experimental

2.1. Crystal data

[Ag₂Mn(CN)₄(C₁₀H₈N₂)]
M_r = 530.94
Trigonal, P 3₁ 12
a = 8.7215 (3) Å
c = 20.9874 (9) Å
V = 1382.52 (13) Å³
Z = 3
Mo Kα radiation
μ = 2.78 mm⁻¹
T = 296 K
0.36 × 0.22 × 0.22 mm

2.2. Data collection

Bruker D8 QUEST CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker,2014 ) T_min = 0.484, T_max = 0.542
25845 measured reflections
1874 independent reflections
1856 reflections with I > 2σ(I)
R_int = 0.024

2.3. Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.038
S = 1.07
1874 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack x determined using 824 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter: 0.037 (6)

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 1422937

Crystal structure: contains datablock I. DOI: 10.1107/S205698901501676X/vn2098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901501676X/vn2098Isup2.hkl

Supporting information file. DOI: 10.1107/S205698901501676X/vn2098Isup3.cdx

checkCIF report

Synthesis and crystallization top

Mn(NO₃)₂·6H₂O (62 mg, 0.5 mmol) and 2,2'-bipyridine (162 mg, 0.5 mmol) were dissolved in 4 ml of a mixture H₂O/CH₃OH (1:1) to form a bright yellow solution and this was pipetted into one side of the H-tube. K[Ag(CN)₂] (250 mg, 2 mmol) was dissolved in 4 mL of a mixture H₂O/CH₃OH to give a colorless solution and this was pipetted into the other side arm of the H-tube. The H-tube was then carefully filled with a mixture H₂O/CH₃OH. Upon slow diffusion for 3 days, pale-yellow block shaped single crystals of the title compound were formed in the manganese(II)-containing side of the H-tube. Yield: 49 mg, 89% based on manganese source.

Refinement top

The C–bound hydrogen atoms were placed in geometrically idealized positions based on chemical coordinations and constrained to ride on their parent atom positions with a C—H distances of 0.93 Å and with U_iso(H) = 1.2U_eq(C) for the aromatic H atoms.

Related literature top

For related crystal structures, see: Soma et al. (1994); Guo et al. (2009). For the use of [Ag(CN)₂]^- as a building block for the construction of cyanide-bridged silver(I)–iron(II) spin-crossover coordination polymers, see: Shorrock et al. (2002); Galet et al. (2003); Niel et al. (2003); Muñoz et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. Displacement ellipsoid plot at the 35% probability level of the immediate coordination geometry about the manganese(II) centre in the title compound. The asymmetric unit is labelled. [Symmetry codes: (i) x, -1 + x – y, 2 – z; (ii) 1 – y, x – y, 1/3 + z; (iii) 1 – y, –x, 5/3 – z].
	Fig. 2. Crystal packing of the title compound viewed along c axis.

Poly[(2,2'-bipyridine-κ²N,N')tetra-µ₂-cyanido-κ⁴C:N;κ⁴N:C-manganese(II)disilver(I)] top

Crystal data top

[Ag₂Mn(CN)₄(C₁₀H₈N₂)]	D_x = 1.913 Mg m⁻³
M_r = 530.94	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁12	Cell parameters from 720 reflections
a = 8.7215 (3) Å	θ = 3.3–26.3°
c = 20.9874 (9) Å	µ = 2.78 mm⁻¹
V = 1382.52 (13) Å³	T = 296 K
Z = 3	Block, light yellow
F(000) = 759	0.36 × 0.22 × 0.22 mm

Data collection top

Bruker D8 QUEST CMOS diffractometer	1874 independent reflections
Radiation source: microfocus sealed x-ray tube, Incoatec Iµus	1856 reflections with I > 2σ(I)
GraphiteDouble Bounce Multilayer Mirror monochromator	R_int = 0.024
Detector resolution: 10.5 pixels mm^-1	θ_max = 26.3°, θ_min = 3.3°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker,2014)	k = −10→10
T_min = 0.484, T_max = 0.542	l = −26→26
25845 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.015	w = 1/[σ²(F_o²) + (0.0231P)² + 0.1949P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.038	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.15 e Å⁻³
1874 reflections	Δρ_min = −0.28 e Å⁻³
105 parameters	Absolute structure: Flack x determined using 824 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.037 (6)
Primary atom site location: structure-invariant direct methods

Crystal data top

[Ag₂Mn(CN)₄(C₁₀H₈N₂)]	Z = 3
M_r = 530.94	Mo Kα radiation
Trigonal, P3₁12	µ = 2.78 mm⁻¹
a = 8.7215 (3) Å	T = 296 K
c = 20.9874 (9) Å	0.36 × 0.22 × 0.22 mm
V = 1382.52 (13) Å³

Data collection top

Bruker D8 QUEST CMOS diffractometer	1874 independent reflections
Absorption correction: multi-scan (SADABS; Bruker,2014)	1856 reflections with I > 2σ(I)
T_min = 0.484, T_max = 0.542	R_int = 0.024
25845 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	H-atom parameters constrained
wR(F²) = 0.038	Δρ_max = 0.15 e Å⁻³
S = 1.07	Δρ_min = −0.28 e Å⁻³
1874 reflections	Absolute structure: Flack x determined using 824 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
105 parameters	Absolute structure parameter: 0.037 (6)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ag1	0.46725 (4)	0.05832 (4)	0.84789 (2)	0.07435 (11)
Mn1	0.89941 (6)	−0.05030 (3)	1.0000	0.03424 (11)
N2	0.2249 (4)	0.0953 (4)	0.74313 (13)	0.0600 (6)
N3	1.1424 (3)	0.1907 (3)	0.96099 (11)	0.0511 (5)
N1	0.7178 (3)	−0.0053 (4)	0.94131 (11)	0.0547 (6)
C7	1.3017 (3)	0.2186 (3)	0.97859 (12)	0.0438 (5)
C4	1.2821 (5)	0.4635 (6)	0.9044 (3)	0.0981 (17)
H4	1.2710	0.5468	0.8803	0.118*
C2	0.3101 (5)	0.0826 (5)	0.78142 (16)	0.0638 (8)
C1	0.6284 (4)	0.0198 (5)	0.90861 (14)	0.0612 (7)
C6	1.4560 (4)	0.3673 (4)	0.95830 (15)	0.0599 (7)
H6	1.5658	0.3828	0.9698	0.072*
C3	1.1344 (5)	0.3099 (6)	0.9239 (2)	0.0848 (13)
H3	1.0238	0.2887	0.9106	0.102*
C5	1.4453 (4)	0.4911 (5)	0.92118 (18)	0.0807 (11)
H5	1.5474	0.5920	0.9077	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ag1	0.0916 (2)	0.1011 (2)	0.05771 (15)	0.06867 (18)	−0.02819 (13)	−0.00888 (13)
Mn1	0.0307 (2)	0.03718 (18)	0.0327 (2)	0.01535 (11)	0.000	−0.00120 (16)
N2	0.0675 (15)	0.0575 (14)	0.0588 (14)	0.0342 (13)	−0.0179 (12)	0.0000 (12)
N3	0.0375 (11)	0.0535 (13)	0.0546 (12)	0.0170 (9)	0.0022 (9)	0.0141 (10)
N1	0.0530 (13)	0.0719 (16)	0.0470 (12)	0.0371 (12)	−0.0084 (10)	−0.0012 (12)
C7	0.0365 (11)	0.0497 (13)	0.0359 (11)	0.0146 (10)	0.0005 (9)	−0.0054 (9)
C4	0.063 (2)	0.080 (3)	0.124 (4)	0.0157 (19)	0.000 (2)	0.056 (3)
C2	0.0752 (19)	0.0685 (19)	0.0578 (17)	0.0435 (17)	−0.0227 (14)	−0.0033 (14)
C1	0.0654 (18)	0.081 (2)	0.0514 (15)	0.0473 (18)	−0.0097 (13)	−0.0030 (14)
C6	0.0363 (13)	0.0621 (17)	0.0594 (16)	0.0082 (12)	−0.0054 (11)	0.0016 (13)
C3	0.0467 (17)	0.082 (2)	0.109 (3)	0.0199 (17)	−0.0021 (18)	0.050 (2)
C5	0.0511 (17)	0.064 (2)	0.088 (2)	−0.0001 (14)	0.0002 (16)	0.0260 (18)

Geometric parameters (Å, º) top

Ag1—C2	2.039 (3)	N3—C3	1.328 (4)
Ag1—C1	2.046 (3)	N1—C1	1.139 (4)
Mn1—N2ⁱ	2.229 (3)	C7—C7ⁱⁱⁱ	1.485 (5)
Mn1—N2ⁱⁱ	2.229 (3)	C7—C6	1.388 (4)
Mn1—N3ⁱⁱⁱ	2.264 (2)	C4—H4	0.9300
Mn1—N3	2.264 (2)	C4—C3	1.377 (5)
Mn1—N1ⁱⁱⁱ	2.192 (2)	C4—C5	1.365 (6)
Mn1—N1	2.192 (2)	C6—H6	0.9300
N2—Mn1^iv	2.229 (3)	C6—C5	1.372 (5)
N2—C2	1.137 (4)	C3—H3	0.9300
N3—C7	1.337 (3)	C5—H5	0.9300

C2—Ag1—C1	174.70 (14)	C3—N3—C7	118.4 (2)
N2ⁱ—Mn1—N2ⁱⁱ	177.94 (15)	C1—N1—Mn1	177.0 (3)
N2ⁱⁱ—Mn1—N3	85.78 (10)	N3—C7—C7ⁱⁱⁱ	115.84 (15)
N2ⁱⁱ—Mn1—N3ⁱⁱⁱ	92.55 (10)	N3—C7—C6	121.3 (3)
N2ⁱ—Mn1—N3ⁱⁱⁱ	85.78 (10)	C6—C7—C7ⁱⁱⁱ	122.90 (17)
N2ⁱ—Mn1—N3	92.55 (10)	C3—C4—H4	120.6
N3ⁱⁱⁱ—Mn1—N3	71.65 (12)	C5—C4—H4	120.6
N1ⁱⁱⁱ—Mn1—N2ⁱ	92.34 (11)	C5—C4—C3	118.7 (4)
N1—Mn1—N2ⁱ	88.95 (10)	N2—C2—Ag1	178.2 (3)
N1—Mn1—N2ⁱⁱ	92.34 (10)	N1—C1—Ag1	178.1 (3)
N1ⁱⁱⁱ—Mn1—N2ⁱⁱ	88.94 (10)	C7—C6—H6	120.2
N1—Mn1—N3	93.18 (10)	C5—C6—C7	119.6 (3)
N1ⁱⁱⁱ—Mn1—N3	163.66 (9)	C5—C6—H6	120.2
N1ⁱⁱⁱ—Mn1—N3ⁱⁱⁱ	93.18 (10)	N3—C3—C4	123.1 (3)
N1—Mn1—N3ⁱⁱⁱ	163.66 (9)	N3—C3—H3	118.5
N1ⁱⁱⁱ—Mn1—N1	102.49 (15)	C4—C3—H3	118.5
C2—N2—Mn1^iv	176.1 (3)	C4—C5—C6	118.9 (3)
C7—N3—Mn1	118.32 (18)	C4—C5—H5	120.6
C3—N3—Mn1	123.2 (2)	C6—C5—H5	120.6

Mn1—N3—C7—C7ⁱⁱⁱ	1.5 (4)	C7—C6—C5—C4	−0.8 (7)
Mn1—N3—C7—C6	−177.6 (2)	C3—N3—C7—C7ⁱⁱⁱ	178.4 (4)
Mn1—N3—C3—C4	174.7 (5)	C3—N3—C7—C6	−0.7 (5)
N3—C7—C6—C5	2.2 (5)	C3—C4—C5—C6	−1.8 (9)
C7—N3—C3—C4	−2.0 (7)	C5—C4—C3—N3	3.3 (10)
C7ⁱⁱⁱ—C7—C6—C5	−176.9 (4)

Symmetry codes: (i) −y+1, −x, −z+5/3; (ii) −y+1, x−y, z+1/3; (iii) x, x−y−1, −z+2; (iv) −x+y+1, −x+1, z−1/3.

Experimental details

Crystal data
Chemical formula	[Ag₂Mn(CN)₄(C₁₀H₈N₂)]
M_r	530.94
Crystal system, space group	Trigonal, P3₁12
Temperature (K)	296
a, c (Å)	8.7215 (3), 20.9874 (9)
V (Å³)	1382.52 (13)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	2.78
Crystal size (mm)	0.36 × 0.22 × 0.22

Data collection
Diffractometer	Bruker D8 QUEST CMOS diffractometer
Absorption correction	Multi-scan (SADABS; Bruker,2014)
T_min, T_max	0.484, 0.542
No. of measured, independent and observed [I > 2σ(I)] reflections	25845, 1874, 1856
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.038, 1.07
No. of reflections	1874
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.28
Absolute structure	Flack x determined using 824 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	0.037 (6)

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Acknowledgements

This research was supported financially by a research career development grant (No. RSA5780056) from the Thailand Research Fund.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (2014). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Galet, A., Niel, V., Muñoz, M. C. & Real, J. A. (2003). J. Am. Chem. Soc. 125, 14224–14225. Web of Science CSD CrossRef PubMed CAS Google Scholar
Guo, Y., Liu, Z.-Q., Zhao, B., Feng, Y.-H., Xu, G.-F., Yan, S.-P., Cheng, P., Wang, Q.-L. & Liao, D.-Z. (2009). CrystEngComm, 11, 61–66. CSD CrossRef CAS Google Scholar
Muñoz, M. C., Gaspar, A. B., Galet, A. & Real, J. A. (2007). Inorg. Chem. 46, 8182–8192. PubMed Google Scholar
Niel, V., Thompson, A. L., Muñoz, M. C., Galet, A., Goeta, A. E. & Real, J. A. (2003). Angew. Chem. Int. Ed. 42, 3760–3763. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shorrock, C. J., Xue, B.-Y., Kim, P. B., Batchelor, R. J., Patrick, B. O. & Leznoff, D. B. (2002). Inorg. Chem. 41, 6743–6753. CSD CrossRef PubMed CAS Google Scholar
Soma, T., Yuge, H. & Iwamoto, T. (1994). Angew. Chem. Int. Ed. Engl. 33, 1665–1666. CSD CrossRef Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages m179-m180

doi:10.1107/S205698901501676X

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