Hydrothermal reaction of Mn2+ with the ditopic ligand 2,5-bis(1H-1,2,4-triazol-1-yl)benzoic acid (Hdtba) resulted in the complex poly[aqua[μ3-2,5-bis(1H-1,2,4-triazol-1-yl)benzoato-κ3N4:N4′:O]chloridomanganese(II)] monohydrate], {[Mn(C11H7N6O2)Cl(H2O)]·H2O}n, (I). Coordination polymer I has been characterized by X-ray diffraction, IR spectroscopy, elemental analysis, thermogravimetry and susceptibility measurements. The topology of I corresponds to a three-dimensional (3,6)-conn net linked by {Mn2Cl2(COO)2} building blocks and dtba− anions. Significant antiferromagnetic exchange is observed within the dinuclear {Mn2Cl2(COO)2} subunits. A fit of the susceptibility data resulted in the magnetic parameters g = 1.93 and J = −1.52. Studies of the photoluminescence properties revealed that I represents a promising luminescence sensor for sensitively detecting dichromate ions in aqueous solution. The associated photochemical detection mechanism was studied in detail.
Supporting information
CCDC reference: 2120639
Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b).
Poly[aqua[µ
3-2,5-bis(1
H-1,2,4-triazol-1-yl)benzoato-
κ3N4:
N4':
O]chloridomanganese(II)] monohydrate]
top
Crystal data top
[Mn(C11H7N6O2)Cl(H2O)]·H2O | F(000) = 772 |
Mr = 381.65 | Dx = 1.777 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0241 (14) Å | Cell parameters from 6145 reflections |
b = 18.827 (3) Å | θ = 2.9–26.5° |
c = 6.8810 (11) Å | µ = 1.14 mm−1 |
β = 92.816 (4)° | T = 296 K |
V = 1426.4 (4) Å3 | Block, colorless |
Z = 4 | 0.35 × 0.33 × 0.32 mm |
Data collection top
Bruker APEXII CCD diffractometer | 2057 reflections with I > 2σ(I) |
ω scans | Rint = 0.067 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | θmax = 26.7°, θmin = 2.9° |
Tmin = 0.685, Tmax = 0.745 | h = −13→13 |
17646 measured reflections | k = −23→23 |
3004 independent reflections | l = −8→8 |
Refinement top
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0296P)2 + 1.953P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3004 reflections | Δρmax = 0.44 e Å−3 |
208 parameters | Δρmin = −0.43 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Diffraction data of I were collected on Bruker Smart Apex diffractometer
at room temperature using Mo-Kα radiation (λ = 0.71073 Å).
Data reduction and absorption correction were completed with SAINT and SADABS
(Bruker, 2012; Bruker, 2001). The structure was solved by intrinsic phasing
with SHELXT-2014. The full matrix least squares refinement was conducted with
the program SHELXL-2018 (Sheldrick, 2015a; Sheldrick, 2015b). All non-H atoms
were refined anisotropically. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.14253 (4) | 0.53134 (3) | 0.36674 (8) | 0.02219 (16) | |
Cl1 | −0.03902 (7) | 0.44803 (5) | 0.30283 (13) | 0.0304 (2) | |
N1 | 0.7188 (2) | 0.38669 (14) | 0.5341 (4) | 0.0287 (7) | |
N2 | 0.6506 (3) | 0.29152 (16) | 0.3659 (5) | 0.0377 (8) | |
N3 | 0.5590 (2) | 0.32306 (14) | 0.4608 (4) | 0.0222 (6) | |
N4 | 0.1030 (2) | 0.19350 (14) | 0.3761 (4) | 0.0221 (6) | |
N5 | −0.0400 (2) | 0.12100 (14) | 0.2770 (4) | 0.0241 (7) | |
N6 | −0.0010 (2) | 0.22245 (15) | 0.4403 (5) | 0.0337 (8) | |
O1 | 0.2515 (2) | 0.44655 (12) | 0.4801 (3) | 0.0278 (6) | |
O2 | 0.4120 (2) | 0.44183 (13) | 0.2949 (4) | 0.0425 (7) | |
O3 | 0.2076 (2) | 0.51490 (16) | 0.0768 (4) | 0.0569 (9) | |
H3A | 0.275665 | 0.507914 | 0.037664 | 0.085* | |
H3B | 0.164403 | 0.527945 | −0.016820 | 0.085* | |
O4 | 0.6080 (3) | 0.51358 (18) | 0.1664 (4) | 0.0669 (10) | |
H4A | 0.556576 | 0.482439 | 0.175947 | 0.100* | |
H4B | 0.648887 | 0.514243 | 0.269332 | 0.100* | |
C1 | 0.7433 (3) | 0.33200 (19) | 0.4147 (6) | 0.0397 (10) | |
H1 | 0.820468 | 0.323835 | 0.370685 | 0.048* | |
C2 | 0.6019 (3) | 0.37902 (17) | 0.5602 (5) | 0.0250 (8) | |
H2 | 0.556169 | 0.408416 | 0.636835 | 0.030* | |
C3 | 0.4399 (3) | 0.29276 (17) | 0.4447 (5) | 0.0202 (7) | |
C4 | 0.3365 (3) | 0.33452 (16) | 0.4213 (5) | 0.0191 (7) | |
C5 | 0.2242 (3) | 0.30049 (17) | 0.4023 (5) | 0.0201 (7) | |
H5 | 0.153326 | 0.327203 | 0.388040 | 0.024* | |
C6 | 0.2179 (3) | 0.22760 (17) | 0.4045 (5) | 0.0200 (7) | |
C7 | 0.3211 (3) | 0.18645 (17) | 0.4314 (5) | 0.0238 (8) | |
H7 | 0.315399 | 0.137182 | 0.434979 | 0.029* | |
C8 | 0.4325 (3) | 0.21940 (17) | 0.4530 (5) | 0.0236 (8) | |
H8 | 0.502688 | 0.192420 | 0.473186 | 0.028* | |
C9 | 0.3357 (3) | 0.41449 (18) | 0.3958 (5) | 0.0235 (8) | |
C10 | 0.0777 (3) | 0.13384 (17) | 0.2793 (5) | 0.0232 (8) | |
H10 | 0.134601 | 0.105279 | 0.221651 | 0.028* | |
C11 | −0.0833 (3) | 0.17696 (19) | 0.3772 (6) | 0.0327 (9) | |
H11 | −0.165287 | 0.182470 | 0.399297 | 0.039* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0171 (3) | 0.0176 (3) | 0.0314 (3) | 0.0013 (2) | −0.0033 (2) | 0.0028 (2) |
Cl1 | 0.0279 (5) | 0.0308 (5) | 0.0323 (5) | −0.0078 (4) | −0.0009 (4) | −0.0019 (4) |
N1 | 0.0176 (15) | 0.0216 (16) | 0.046 (2) | −0.0010 (12) | −0.0022 (13) | −0.0047 (15) |
N2 | 0.0224 (15) | 0.0307 (17) | 0.061 (2) | −0.0034 (14) | 0.0133 (15) | −0.0156 (17) |
N3 | 0.0148 (14) | 0.0210 (15) | 0.0306 (17) | 0.0006 (12) | 0.0000 (12) | −0.0039 (13) |
N4 | 0.0187 (14) | 0.0192 (15) | 0.0283 (17) | −0.0030 (12) | 0.0020 (12) | −0.0058 (13) |
N5 | 0.0175 (14) | 0.0206 (16) | 0.0341 (18) | −0.0027 (12) | 0.0008 (12) | −0.0059 (13) |
N6 | 0.0217 (15) | 0.0296 (17) | 0.051 (2) | −0.0037 (13) | 0.0095 (14) | −0.0146 (15) |
O1 | 0.0268 (13) | 0.0210 (13) | 0.0357 (15) | 0.0069 (10) | 0.0015 (11) | −0.0002 (11) |
O2 | 0.0278 (13) | 0.0366 (16) | 0.064 (2) | −0.0022 (12) | 0.0118 (13) | 0.0192 (14) |
O3 | 0.0419 (16) | 0.097 (3) | 0.0317 (17) | 0.0306 (16) | −0.0004 (13) | 0.0035 (16) |
O4 | 0.0548 (19) | 0.088 (3) | 0.058 (2) | −0.0243 (18) | 0.0078 (16) | 0.0058 (19) |
C1 | 0.0186 (19) | 0.030 (2) | 0.071 (3) | −0.0011 (16) | 0.0105 (18) | −0.011 (2) |
C2 | 0.0203 (17) | 0.0213 (19) | 0.033 (2) | 0.0029 (15) | −0.0039 (15) | −0.0049 (16) |
C3 | 0.0170 (16) | 0.0236 (19) | 0.0195 (19) | −0.0027 (14) | −0.0023 (14) | −0.0011 (15) |
C4 | 0.0222 (17) | 0.0191 (17) | 0.0159 (18) | −0.0011 (14) | −0.0009 (14) | −0.0009 (14) |
C5 | 0.0182 (16) | 0.0195 (18) | 0.0227 (19) | 0.0004 (13) | 0.0015 (14) | −0.0026 (15) |
C6 | 0.0185 (16) | 0.0224 (19) | 0.0191 (18) | −0.0044 (14) | −0.0003 (14) | −0.0030 (15) |
C7 | 0.0265 (18) | 0.0156 (17) | 0.029 (2) | −0.0019 (15) | −0.0037 (15) | −0.0031 (15) |
C8 | 0.0217 (17) | 0.0215 (19) | 0.027 (2) | 0.0037 (14) | −0.0038 (15) | −0.0028 (16) |
C9 | 0.0186 (17) | 0.0239 (19) | 0.027 (2) | −0.0015 (15) | −0.0071 (15) | 0.0042 (16) |
C10 | 0.0221 (18) | 0.0205 (19) | 0.027 (2) | 0.0000 (14) | 0.0025 (15) | −0.0055 (16) |
C11 | 0.0201 (18) | 0.030 (2) | 0.049 (3) | −0.0021 (16) | 0.0081 (17) | −0.0112 (19) |
Geometric parameters (Å, º) top
Mn1—O1 | 2.123 (2) | O2—C9 | 1.230 (4) |
Mn1—O3 | 2.175 (3) | O3—H3A | 0.8198 |
Mn1—N5i | 2.235 (3) | O3—H3B | 0.8197 |
Mn1—N1ii | 2.254 (3) | O4—H4A | 0.8205 |
Mn1—Cl1 | 2.5637 (10) | O4—H4B | 0.8205 |
Mn1—Cl1iii | 2.6225 (11) | C1—H1 | 0.9300 |
N1—C2 | 1.318 (4) | C2—H2 | 0.9300 |
N1—C1 | 1.353 (4) | C3—C8 | 1.385 (5) |
N2—C1 | 1.306 (4) | C3—C4 | 1.387 (4) |
N2—N3 | 1.365 (4) | C4—C5 | 1.395 (4) |
N3—C2 | 1.330 (4) | C4—C9 | 1.516 (4) |
N3—C3 | 1.431 (4) | C5—C6 | 1.374 (4) |
N4—C10 | 1.329 (4) | C5—H5 | 0.9300 |
N4—N6 | 1.363 (4) | C6—C7 | 1.381 (4) |
N4—C6 | 1.425 (4) | C7—C8 | 1.378 (4) |
N5—C10 | 1.319 (4) | C7—H7 | 0.9300 |
N5—C11 | 1.358 (4) | C8—H8 | 0.9300 |
N6—C11 | 1.306 (4) | C10—H10 | 0.9300 |
O1—C9 | 1.271 (4) | C11—H11 | 0.9300 |
| | | |
O1—Mn1—O3 | 91.36 (10) | H4A—O4—H4B | 107.1 |
O1—Mn1—N5i | 174.33 (10) | N2—C1—N1 | 115.1 (3) |
O3—Mn1—N5i | 83.33 (10) | N2—C1—H1 | 122.5 |
O1—Mn1—N1ii | 92.31 (9) | N1—C1—H1 | 122.5 |
O3—Mn1—N1ii | 97.21 (11) | N1—C2—N3 | 110.0 (3) |
N5i—Mn1—N1ii | 86.41 (10) | N1—C2—H2 | 125.0 |
O1—Mn1—Cl1 | 91.50 (7) | N3—C2—H2 | 125.0 |
O3—Mn1—Cl1 | 92.61 (8) | C8—C3—C4 | 121.4 (3) |
N5i—Mn1—Cl1 | 90.73 (7) | C8—C3—N3 | 116.7 (3) |
N1ii—Mn1—Cl1 | 169.37 (8) | C4—C3—N3 | 121.9 (3) |
O1—Mn1—Cl1iii | 93.18 (7) | C3—C4—C5 | 118.1 (3) |
O3—Mn1—Cl1iii | 173.44 (7) | C3—C4—C9 | 125.2 (3) |
N5i—Mn1—Cl1iii | 92.28 (8) | C5—C4—C9 | 116.4 (3) |
N1ii—Mn1—Cl1iii | 87.35 (8) | C6—C5—C4 | 120.2 (3) |
Cl1—Mn1—Cl1iii | 82.53 (3) | C6—C5—H5 | 119.9 |
Mn1—Cl1—Mn1iii | 97.46 (3) | C4—C5—H5 | 119.9 |
C2—N1—C1 | 103.0 (3) | C5—C6—C7 | 121.3 (3) |
C2—N1—Mn1ii | 133.4 (2) | C5—C6—N4 | 119.6 (3) |
C1—N1—Mn1ii | 123.5 (2) | C7—C6—N4 | 119.1 (3) |
C1—N2—N3 | 102.2 (3) | C8—C7—C6 | 119.1 (3) |
C2—N3—N2 | 109.7 (3) | C8—C7—H7 | 120.5 |
C2—N3—C3 | 131.1 (3) | C6—C7—H7 | 120.5 |
N2—N3—C3 | 119.1 (3) | C7—C8—C3 | 119.9 (3) |
C10—N4—N6 | 109.9 (2) | C7—C8—H8 | 120.1 |
C10—N4—C6 | 127.8 (3) | C3—C8—H8 | 120.1 |
N6—N4—C6 | 122.1 (3) | O2—C9—O1 | 126.4 (3) |
C10—N5—C11 | 102.8 (3) | O2—C9—C4 | 118.7 (3) |
C10—N5—Mn1iv | 128.3 (2) | O1—C9—C4 | 114.8 (3) |
C11—N5—Mn1iv | 128.9 (2) | N5—C10—N4 | 110.1 (3) |
C11—N6—N4 | 102.2 (3) | N5—C10—H10 | 125.0 |
C9—O1—Mn1 | 127.0 (2) | N4—C10—H10 | 125.0 |
Mn1—O3—H3A | 132.2 | N6—C11—N5 | 115.0 (3) |
Mn1—O3—H3B | 118.2 | N6—C11—H11 | 122.5 |
H3A—O3—H3B | 107.2 | N5—C11—H11 | 122.5 |
| | | |
C1—N2—N3—C2 | −0.6 (4) | C10—N4—C6—C5 | 142.6 (3) |
C1—N2—N3—C3 | −179.2 (3) | N6—N4—C6—C5 | −33.5 (5) |
C10—N4—N6—C11 | 0.3 (4) | C10—N4—C6—C7 | −36.7 (5) |
C6—N4—N6—C11 | 177.0 (3) | N6—N4—C6—C7 | 147.3 (3) |
N3—N2—C1—N1 | 0.4 (4) | C5—C6—C7—C8 | −1.2 (5) |
C2—N1—C1—N2 | 0.0 (5) | N4—C6—C7—C8 | 178.1 (3) |
Mn1ii—N1—C1—N2 | −177.1 (3) | C6—C7—C8—C3 | −0.9 (5) |
C1—N1—C2—N3 | −0.3 (4) | C4—C3—C8—C7 | 2.2 (5) |
Mn1ii—N1—C2—N3 | 176.4 (2) | N3—C3—C8—C7 | −177.7 (3) |
N2—N3—C2—N1 | 0.6 (4) | Mn1—O1—C9—O2 | 40.4 (5) |
C3—N3—C2—N1 | 179.0 (3) | Mn1—O1—C9—C4 | −137.8 (2) |
C2—N3—C3—C8 | −137.1 (4) | C3—C4—C9—O2 | 39.2 (5) |
N2—N3—C3—C8 | 41.2 (4) | C5—C4—C9—O2 | −134.9 (3) |
C2—N3—C3—C4 | 43.1 (5) | C3—C4—C9—O1 | −142.5 (3) |
N2—N3—C3—C4 | −138.6 (3) | C5—C4—C9—O1 | 43.4 (4) |
C8—C3—C4—C5 | −1.3 (5) | C11—N5—C10—N4 | 0.4 (4) |
N3—C3—C4—C5 | 178.6 (3) | Mn1iv—N5—C10—N4 | 178.3 (2) |
C8—C3—C4—C9 | −175.3 (3) | N6—N4—C10—N5 | −0.5 (4) |
N3—C3—C4—C9 | 4.6 (5) | C6—N4—C10—N5 | −176.9 (3) |
C3—C4—C5—C6 | −0.8 (5) | N4—N6—C11—N5 | −0.1 (4) |
C9—C4—C5—C6 | 173.7 (3) | C10—N5—C11—N6 | −0.2 (4) |
C4—C5—C6—C7 | 2.1 (5) | Mn1iv—N5—C11—N6 | −178.1 (2) |
C4—C5—C6—N4 | −177.2 (3) | | |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2 | 0.82 | 2.58 | 2.982 (4) | 111 |
O3—H3B···Cl1v | 0.82 | 2.39 | 3.208 (3) | 173 |
O3—H3B···N5i | 0.82 | 2.81 | 2.932 (4) | 90 |
O4—H4A···O2 | 0.82 | 1.98 | 2.732 (4) | 152 |
O4—H4B···O1ii | 0.82 | 2.13 | 2.917 (4) | 161 |
C1—H1···Cl1vi | 0.93 | 2.86 | 3.362 (4) | 116 |
C7—H7···O4vii | 0.93 | 2.58 | 3.422 (5) | 150 |
C10—H10···O1viii | 0.93 | 2.36 | 3.255 (4) | 160 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (v) −x, −y+1, −z; (vi) x+1, y, z; (vii) −x+1, y−1/2, −z+1/2; (viii) x, −y+1/2, z−1/2. |