The crystal structure, luminescence and nitro­benzene-sensing properties of a two-dimensional Mn^II coordination polymer based on 2,6-bis­(imidazol-1-yl)pyridine

A two-dimensional Mn^II coordination polymer (CP), poly[bis­[μ₂-2,6-bis­(imid­azol-1-yl)pyridine-κ²N³:N^3′]bis­(thio­cyanato-κN)manganese] [Mn(NCS)₂(C₁₁H₉N₅)₂]_n, (I), has been obtained by the self-assembly reaction of Mn(ClO₄)₂·6H₂O, NH₄SCN and bent 2,6-bis­(imidazol-1-yl)pyridine (2,6-bip). CP (I) was characterized by FT–IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal structure features a unique two-dimensional (4,4) network with one-dimensional channels. The luminescence and nitro­benzene-sensing properties were explored in a DMF suspension, revealing that CP (I) shows a strong luminescence emission and is highly sensitive for nitro­benzene detection.

Computing details

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[bis[µ₂-2,6-bis(imidazol-1-yl)pyridine-κ²N³:N^3']bis(thiocyanato-κN)manganese]

Crystal data

[Mn(NCS)2(C11H9N5)2]	F(000) = 606
Mr = 593.56	Dx = 1.490 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.162 (2) Å	Cell parameters from 5437 reflections
b = 9.1537 (18) Å	θ = 2.9–28.8°
c = 16.348 (5) Å	µ = 0.70 mm^−1
β = 127.64 (2)°	T = 150 K
V = 1322.7 (6) Å^3	Block, colorless
Z = 2	0.17 × 0.14 × 0.12 mm

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2169 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
dtprofit.ref [Scan method?] scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −11→13
Tmin = 0.891, Tmax = 0.921	k = −11→11
5951 measured reflections	l = −19→13
2510 independent reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.3427P] where P = (Fo^2 + 2Fc^2)/3
2510 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.46 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
Mn1	0.5000	0.5000	0.5000	0.02128 (13)
S1	0.81608 (7)	0.46962 (7)	0.87351 (4)	0.04584 (19)
N1	0.65366 (18)	0.54780 (19)	0.66632 (12)	0.0318 (4)
N2	0.57121 (17)	0.26101 (17)	0.53144 (11)	0.0247 (4)
N3	0.70992 (16)	0.07056 (16)	0.62555 (11)	0.0213 (3)
N4	0.76649 (16)	0.52693 (16)	0.27661 (12)	0.0226 (3)
N5	0.81056 (16)	0.60929 (16)	0.42664 (11)	0.0221 (3)
N6	0.67951 (17)	0.55953 (17)	0.48336 (12)	0.0248 (4)
C1	0.7205 (2)	0.51519 (19)	0.75239 (15)	0.0233 (4)
C2	0.63745 (19)	0.1935 (2)	0.62052 (14)	0.0226 (4)
H2	0.6349	0.2266	0.6745	0.027*
C3	0.6862 (2)	0.0586 (2)	0.53229 (14)	0.0266 (4)
H3	0.7227	−0.0159	0.5123	0.032*
C4	0.6003 (2)	0.1747 (2)	0.47562 (14)	0.0271 (4)
H4	0.5648	0.1945	0.4071	0.032*
C10	0.6894 (2)	0.5380 (2)	0.40831 (14)	0.0244 (4)
H5	0.6209	0.4801	0.3489	0.029*
C12	0.7993 (2)	0.6490 (2)	0.55326 (15)	0.0271 (4)
H6	0.8212	0.6832	0.6160	0.033*
C11	0.8813 (2)	0.6813 (2)	0.51993 (14)	0.0271 (4)
H7	0.9691	0.7409	0.5536	0.033*
C9	0.8566 (2)	0.60534 (19)	0.36256 (14)	0.0223 (4)
C8	0.9847 (2)	0.6783 (2)	0.38965 (15)	0.0270 (4)
H9	1.0430	0.7366	0.4502	0.032*
C7	1.0241 (2)	0.6626 (2)	0.32485 (15)	0.0288 (4)
H10	1.1126	0.7092	0.3414	0.035*
C6	0.9357 (2)	0.5796 (2)	0.23609 (15)	0.0260 (4)
H11	0.9620	0.5663	0.1912	0.031*
C5	0.8071 (2)	−0.01664 (19)	0.71537 (14)	0.0213 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0227 (2)	0.0263 (2)	0.0152 (2)	0.00274 (17)	0.01176 (18)	0.00251 (16)
S1	0.0646 (4)	0.0456 (4)	0.0224 (3)	0.0179 (3)	0.0240 (3)	0.0109 (2)
N1	0.0334 (9)	0.0380 (10)	0.0205 (9)	0.0010 (8)	0.0147 (8)	0.0015 (7)
N2	0.0254 (8)	0.0271 (8)	0.0221 (8)	0.0017 (7)	0.0148 (7)	0.0026 (7)
N3	0.0225 (8)	0.0217 (8)	0.0219 (8)	−0.0002 (7)	0.0147 (7)	0.0013 (6)
N4	0.0232 (8)	0.0234 (8)	0.0225 (8)	0.0005 (7)	0.0146 (7)	−0.0003 (6)
N5	0.0260 (8)	0.0215 (8)	0.0215 (8)	−0.0033 (7)	0.0158 (7)	−0.0022 (6)
N6	0.0276 (8)	0.0269 (8)	0.0232 (8)	−0.0010 (7)	0.0173 (7)	−0.0014 (7)
C1	0.0240 (9)	0.0230 (9)	0.0248 (11)	−0.0008 (8)	0.0159 (8)	−0.0023 (8)
C2	0.0234 (9)	0.0231 (9)	0.0247 (9)	0.0019 (8)	0.0163 (8)	0.0017 (8)
C3	0.0317 (10)	0.0259 (10)	0.0243 (10)	−0.0022 (9)	0.0183 (9)	−0.0044 (8)
C4	0.0315 (10)	0.0296 (10)	0.0205 (9)	−0.0018 (9)	0.0161 (8)	−0.0016 (8)
C10	0.0241 (10)	0.0285 (10)	0.0222 (9)	−0.0023 (8)	0.0149 (8)	−0.0035 (8)
C12	0.0375 (11)	0.0226 (9)	0.0240 (9)	−0.0043 (9)	0.0201 (9)	−0.0049 (8)
C11	0.0316 (10)	0.0240 (10)	0.0251 (10)	−0.0075 (8)	0.0170 (8)	−0.0063 (8)
C9	0.0250 (9)	0.0200 (9)	0.0227 (9)	0.0021 (8)	0.0150 (8)	0.0015 (8)
C8	0.0244 (9)	0.0259 (10)	0.0283 (10)	−0.0050 (8)	0.0149 (8)	−0.0035 (8)
C7	0.0250 (9)	0.0284 (11)	0.0346 (11)	−0.0050 (8)	0.0190 (9)	0.0011 (9)
C6	0.0273 (10)	0.0273 (10)	0.0284 (10)	0.0020 (9)	0.0196 (8)	0.0041 (8)
C5	0.0222 (9)	0.0204 (9)	0.0213 (9)	−0.0047 (7)	0.0132 (8)	−0.0038 (7)

Geometric parameters (Å, º)

Mn1—N1	2.1977 (18)	N6—C12	1.378 (2)
Mn1—N1^i	2.1978 (18)	C2—H2	0.9500
Mn1—N6	2.2476 (15)	C3—C4	1.349 (3)
Mn1—N6^i	2.2476 (15)	C3—H3	0.9500
Mn1—N2^i	2.2765 (16)	C4—H4	0.9500
Mn1—N2	2.2765 (16)	C10—H5	0.9500
S1—C1	1.629 (2)	C12—C11	1.353 (3)
N1—C1	1.159 (2)	C12—H6	0.9500
N2—C2	1.317 (2)	C11—H7	0.9500
N2—C4	1.388 (2)	C9—C8	1.383 (3)
N3—C2	1.359 (2)	C8—C7	1.381 (3)
N3—C3	1.383 (2)	C8—H9	0.9500
N3—C5	1.423 (2)	C7—C6	1.381 (3)
N4—C5^ii	1.331 (2)	C7—H10	0.9500
N4—C9	1.332 (2)	C6—C5^ii	1.383 (3)
N5—C10	1.360 (2)	C6—H11	0.9500
N5—C11	1.383 (2)	C5—N4^iii	1.331 (2)
N5—C9	1.421 (2)	C5—C6^iii	1.383 (3)
N6—C10	1.313 (2)
N1—Mn1—N1^i	180.0	N3—C2—H2	124.2
N1—Mn1—N6	91.24 (6)	C4—C3—N3	105.82 (16)
N1^i—Mn1—N6	88.76 (6)	C4—C3—H3	127.1
N1—Mn1—N6^i	88.76 (6)	N3—C3—H3	127.1
N1^i—Mn1—N6^i	91.24 (6)	C3—C4—N2	110.48 (16)
N6—Mn1—N6^i	180.0	C3—C4—H4	124.8
N1—Mn1—N2^i	89.38 (6)	N2—C4—H4	124.8
N1^i—Mn1—N2^i	90.62 (6)	N6—C10—N5	111.23 (16)
N6—Mn1—N2^i	87.35 (6)	N6—C10—H5	124.4
N6^i—Mn1—N2^i	92.64 (6)	N5—C10—H5	124.4
N1—Mn1—N2	90.62 (6)	C11—C12—N6	110.38 (16)
N1^i—Mn1—N2	89.38 (6)	C11—C12—H6	124.8
N6—Mn1—N2	92.65 (6)	N6—C12—H6	124.8
N6^i—Mn1—N2	87.35 (6)	C12—C11—N5	105.60 (16)
N2^i—Mn1—N2	180.00 (2)	C12—C11—H7	127.2
C1—N1—Mn1	152.63 (16)	N5—C11—H7	127.2
C2—N2—C4	105.15 (15)	N4—C9—C8	124.37 (17)
C2—N2—Mn1	125.69 (12)	N4—C9—N5	114.30 (15)
C4—N2—Mn1	126.05 (12)	C8—C9—N5	121.33 (16)
C2—N3—C3	106.99 (15)	C7—C8—C9	117.13 (18)
C2—N3—C5	125.29 (15)	C7—C8—H9	121.4
C3—N3—C5	127.25 (15)	C9—C8—H9	121.4
C5^ii—N4—C9	116.56 (15)	C8—C7—C6	120.32 (17)
C10—N5—C11	107.05 (15)	C8—C7—H10	119.8
C10—N5—C9	125.70 (15)	C6—C7—H10	119.8
C11—N5—C9	127.23 (15)	C7—C6—C5^ii	117.10 (17)
C10—N6—C12	105.75 (15)	C7—C6—H11	121.4
C10—N6—Mn1	131.85 (13)	C5^ii—C6—H11	121.4
C12—N6—Mn1	121.94 (12)	N4^iii—C5—C6^iii	124.44 (17)
N1—C1—S1	179.37 (18)	N4^iii—C5—N3	114.86 (15)
N2—C2—N3	111.53 (15)	C6^iii—C5—N3	120.66 (16)
N2—C2—H2	124.2
C4—N2—C2—N3	1.28 (19)	C10—N5—C11—C12	0.3 (2)
Mn1—N2—C2—N3	−159.64 (11)	C9—N5—C11—C12	−177.90 (17)
C3—N3—C2—N2	−0.75 (19)	C5^ii—N4—C9—C8	1.8 (3)
C5—N3—C2—N2	171.91 (15)	C5^ii—N4—C9—N5	−178.24 (15)
C2—N3—C3—C4	−0.13 (19)	C10—N5—C9—N4	2.1 (3)
C5—N3—C3—C4	−172.61 (16)	C11—N5—C9—N4	179.97 (16)
N3—C3—C4—N2	0.9 (2)	C10—N5—C9—C8	−177.93 (18)
C2—N2—C4—C3	−1.4 (2)	C11—N5—C9—C8	−0.1 (3)
Mn1—N2—C4—C3	159.46 (13)	N4—C9—C8—C7	−2.9 (3)
C12—N6—C10—N5	0.1 (2)	N5—C9—C8—C7	177.13 (16)
Mn1—N6—C10—N5	172.29 (12)	C9—C8—C7—C6	1.3 (3)
C11—N5—C10—N6	−0.3 (2)	C8—C7—C6—C5^ii	1.0 (3)
C9—N5—C10—N6	177.95 (16)	C2—N3—C5—N4^iii	35.6 (2)
C10—N6—C12—C11	0.0 (2)	C3—N3—C5—N4^iii	−153.27 (17)
Mn1—N6—C12—C11	−173.08 (13)	C2—N3—C5—C6^iii	−142.32 (18)
N6—C12—C11—N5	−0.2 (2)	C3—N3—C5—C6^iii	28.9 (3)

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