The crystal structure of the title compound, [Mn(NCS)
2(hmt)
2(H
2O)
2]·[Mn(NCS)
2(H
2O)
4]·2H
2O, where hmt is hexamethylenetetramine (C
6H
12N
4), shows that each Mn atom is in an octahedral coordination enviroment, and that the independent uncharged components [Mn(NCS)
2(hmt)
2(H
2O)
2], [Mn(NCS)
2(H
2O)
4] and H
2O are linked together by three kinds of hydrogen bonds (O—H
N, O—H
O and O—H
S) to form a three-dimensional supramolecular structure.
Supporting information
CCDC reference: 162799
Key indicators
- Single-crystal X-ray study
- T = 288 K
- Mean (N-C) = 0.002 Å
- R factor = 0.024
- wR factor = 0.062
- Data-to-parameter ratio = 14.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
PLAT_731 Alert B Bond Calc 0.82(3), Rep 0.819(5) .... 6.00 s.u-Ratio
O4 -H4OA 1.555 1.555
| Author response: Hydrogen atoms sites solution of water was used the method of
difference Fourier map. O-H distance was restraint with "DFix.82"
instruction during the refinement.
|
PLAT_735 Alert B D-H Calc 0.82(3), Rep 0.819(5) .... 6.00 s.u-Ratio
O4 -H4OA 1.555 1.555
| Author response: Hydrogen atoms sites solution of water was used the method of
difference Fourier map. O-H distance was restraint with "DFix.82"
instruction during the refinement.
|
PLAT_736 Alert B H...A Calc 2.00(3), Rep 2.001(6) .... 5.00 s.u-Ratio
H4OA -N4 1.555 1.555
| Author response: Hydrogen atoms sites solution of water was used the method of
difference Fourier map. O-H distance was restraint with "DFix.82"
instruction during the refinement.
|
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor O1 - H1OB ?
PLAT_731 Alert C Bond Calc 0.818(17), Rep 0.818(5) .... 3.40 s.u-Ratio
O1 -H1OA 1.555 1.555
PLAT_731 Alert C Bond Calc 0.82(2), Rep 0.818(5) .... 4.00 s.u-Ratio
O1 -H1OB 1.555 1.555
PLAT_731 Alert C Bond Calc 0.823(18), Rep 0.823(5) .... 3.60 s.u-Ratio
O2 -H2OA 1.555 1.555
PLAT_731 Alert C Bond Calc 0.82(2), Rep 0.822(5) .... 4.00 s.u-Ratio
O2 -H2OB 1.555 1.555
PLAT_731 Alert C Bond Calc 0.815(14), Rep 0.815(5) .... 2.80 s.u-Ratio
O3 -H3OA 1.555 1.555
PLAT_731 Alert C Bond Calc 0.817(12), Rep 0.816(5) .... 2.40 s.u-Ratio
O3 -H3OB 1.555 1.555
PLAT_731 Alert C Bond Calc 0.819(18), Rep 0.818(5) .... 3.60 s.u-Ratio
O4 -H4OB 1.555 1.555
PLAT_735 Alert C D-H Calc 0.819(18), Rep 0.818(5) .... 3.60 s.u-Ratio
O4 -H4OB 1.555 1.555
PLAT_735 Alert C D-H Calc 0.82(2), Rep 0.822(5) .... 4.00 s.u-Ratio
O2 -H2OB 1.555 1.555
PLAT_735 Alert C D-H Calc 0.823(18), Rep 0.823(5) .... 3.60 s.u-Ratio
O2 -H2OA 1.555 1.555
PLAT_735 Alert C D-H Calc 0.817(12), Rep 0.816(5) .... 2.40 s.u-Ratio
O3 -H3OB 1.555 1.555
PLAT_735 Alert C D-H Calc 0.815(14), Rep 0.815(5) .... 2.80 s.u-Ratio
O3 -H3OA 1.555 1.555
PLAT_735 Alert C D-H Calc 0.818(17), Rep 0.818(5) .... 3.40 s.u-Ratio
O1 -H1OA 1.555 1.555
PLAT_736 Alert C H...A Calc 1.991(18), Rep 1.992(7) .... 2.57 s.u-Ratio
H2OA -N3 1.555 1.555
PLAT_736 Alert C H...A Calc 1.925(16), Rep 1.925(6) .... 2.67 s.u-Ratio
H1OA -O4 1.555 2.666
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C16 H40 Mn2 N12 O8 S4
Atom count from _chemical_formula_moiety:C16 H40 Mn1 N12 O8 S4
0 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
16 Alert Level C = Please check
To 1 mmol of hmt and 2 mmol of MnCl2·4H2O in 3.5 ml of water solution,
2 ml aqueous solution of NH4SCN was added and the mixture stirred for
ca 10 min. The resulting solution was allowed to stand for 2 d.
Colorless crystals were collected in 34% yield.
H atoms were placed in calculated positions (C—H = 0.97 Å), assigned fixed
isotropic displacement parameters at 1.2 times the equivalent Uiso of
the atoms to which they are attached and were allowed to ride on their
respective parent atoms.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
[Mn(NCS)2(C6H12N4)2(H2O)2]·[Mn(NCS)2(H2O)4]·2H2O | Z = 1 |
Mr = 766.72 | F(000) = 398 |
Triclinic, P1 | Dx = 1.507 Mg m−3 |
a = 7.969 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.111 (1) Å | Cell parameters from 26 reflections |
c = 13.076 (2) Å | θ = 2.8–17.2° |
α = 94.34 (1)° | µ = 1.05 mm−1 |
β = 96.83 (1)° | T = 288 K |
γ = 115.16 (1)° | Block, colourless |
V = 844.76 (19) Å3 | 0.48 × 0.48 × 0.40 mm |
Data collection top
Siemens P4 diffractometer | 2853 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.010 |
Graphite monochromator | θmax = 26.0°, θmin = 1.6° |
ω scans | h = 0→9 |
Absorption correction: ψ scan (XSCANS; Siemens, 1994) | k = −11→10 |
Tmin = 0.615, Tmax = 0.653 | l = −16→16 |
3694 measured reflections | 3 standard reflections every 97 reflections |
3316 independent reflections | intensity decay: 3.5% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0321P)2 + 0.1263P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3316 reflections | Δρmax = 0.33 e Å−3 |
226 parameters | Δρmin = −0.27 e Å−3 |
12 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0364 (17) |
Crystal data top
[Mn(NCS)2(C6H12N4)2(H2O)2]·[Mn(NCS)2(H2O)4]·2H2O | γ = 115.16 (1)° |
Mr = 766.72 | V = 844.76 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.969 (1) Å | Mo Kα radiation |
b = 9.111 (1) Å | µ = 1.05 mm−1 |
c = 13.076 (2) Å | T = 288 K |
α = 94.34 (1)° | 0.48 × 0.48 × 0.40 mm |
β = 96.83 (1)° | |
Data collection top
Siemens P4 diffractometer | 2853 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1994) | Rint = 0.010 |
Tmin = 0.615, Tmax = 0.653 | 3 standard reflections every 97 reflections |
3694 measured reflections | intensity decay: 3.5% |
3316 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 12 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.33 e Å−3 |
3316 reflections | Δρmin = −0.27 e Å−3 |
226 parameters | |
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. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.5000 | 0.0000 | 0.5000 | 0.02889 (10) | |
Mn2 | 0.0000 | −0.5000 | 0.0000 | 0.03183 (11) | |
S1 | −0.16159 (7) | −0.37686 (7) | 0.44188 (4) | 0.05815 (16) | |
S2 | 0.66791 (6) | −0.21450 (6) | 0.17286 (4) | 0.05044 (14) | |
N1 | 0.42844 (17) | 0.09081 (14) | 0.33825 (9) | 0.0284 (3) | |
N2 | 0.5533 (2) | 0.22801 (17) | 0.19114 (11) | 0.0383 (3) | |
N3 | 0.2372 (2) | 0.00512 (16) | 0.16372 (10) | 0.0354 (3) | |
N4 | 0.3028 (2) | 0.26803 (16) | 0.26084 (11) | 0.0391 (3) | |
N5 | 0.2048 (2) | −0.1341 (2) | 0.49683 (12) | 0.0475 (4) | |
N6 | 0.2969 (2) | −0.37415 (18) | 0.07137 (12) | 0.0453 (4) | |
O1 | 0.4996 (2) | 0.21088 (15) | 0.59150 (10) | 0.0433 (3) | |
O2 | −0.03956 (19) | −0.27697 (16) | 0.03734 (11) | 0.0463 (3) | |
O3 | 0.0833 (2) | −0.4221 (2) | −0.14557 (10) | 0.0612 (4) | |
O4 | 0.1863 (2) | 0.50706 (16) | 0.32481 (11) | 0.0467 (3) | |
C1 | 0.5968 (2) | 0.1713 (2) | 0.28886 (12) | 0.0344 (4) | |
H1A | 0.6912 | 0.2641 | 0.3368 | 0.041* | |
H1B | 0.6490 | 0.0946 | 0.2748 | 0.041* | |
C2 | 0.2858 (2) | −0.04843 (18) | 0.26183 (12) | 0.0337 (4) | |
H2A | 0.3343 | −0.1277 | 0.2473 | 0.040* | |
H2B | 0.1730 | −0.1020 | 0.2919 | 0.040* | |
C3 | 0.3508 (2) | 0.2099 (2) | 0.35709 (12) | 0.0358 (4) | |
H3A | 0.2388 | 0.1591 | 0.3883 | 0.043* | |
H3B | 0.4423 | 0.3030 | 0.4060 | 0.043* | |
C4 | 0.4101 (3) | 0.0862 (2) | 0.11935 (13) | 0.0401 (4) | |
H4A | 0.4601 | 0.0083 | 0.1040 | 0.048* | |
H4B | 0.3802 | 0.1221 | 0.0546 | 0.048* | |
C5 | 0.4729 (3) | 0.3427 (2) | 0.21334 (14) | 0.0440 (4) | |
H5A | 0.4418 | 0.3794 | 0.1491 | 0.053* | |
H5B | 0.5661 | 0.4380 | 0.2600 | 0.053* | |
C6 | 0.1634 (2) | 0.1252 (2) | 0.18730 (14) | 0.0413 (4) | |
H6A | 0.0499 | 0.0732 | 0.2171 | 0.050* | |
H6B | 0.1309 | 0.1617 | 0.1233 | 0.050* | |
C7 | 0.0528 (2) | −0.2347 (2) | 0.47418 (12) | 0.0347 (4) | |
C8 | 0.4509 (2) | −0.30931 (19) | 0.11229 (13) | 0.0330 (3) | |
H1OA | 0.5946 (17) | 0.2925 (18) | 0.6187 (17) | 0.071 (8)* | |
H1OB | 0.4048 (18) | 0.210 (3) | 0.610 (2) | 0.105 (11)* | |
H2OA | 0.0512 (19) | −0.196 (2) | 0.0704 (16) | 0.085 (9)* | |
H2OB | −0.1345 (18) | −0.294 (3) | 0.0629 (17) | 0.085 (9)* | |
H3OA | 0.1931 (10) | −0.367 (2) | −0.1501 (15) | 0.072 (8)* | |
H3OB | 0.013 (2) | −0.457 (2) | −0.2016 (8) | 0.065 (7)* | |
H4OA | 0.215 (4) | 0.436 (2) | 0.3025 (17) | 0.087 (9)* | |
H4OB | 0.145 (3) | 0.488 (3) | 0.3792 (11) | 0.081 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.02875 (18) | 0.02442 (17) | 0.02892 (18) | 0.00741 (14) | 0.00444 (13) | 0.00397 (13) |
Mn2 | 0.02604 (18) | 0.03186 (19) | 0.03127 (19) | 0.00747 (14) | 0.00344 (14) | 0.00213 (14) |
S1 | 0.0347 (3) | 0.0591 (3) | 0.0584 (3) | 0.0038 (2) | 0.0001 (2) | −0.0058 (2) |
S2 | 0.0278 (2) | 0.0529 (3) | 0.0610 (3) | 0.0132 (2) | −0.0016 (2) | −0.0058 (2) |
N1 | 0.0315 (7) | 0.0236 (6) | 0.0278 (6) | 0.0102 (5) | 0.0045 (5) | 0.0029 (5) |
N2 | 0.0368 (8) | 0.0362 (7) | 0.0350 (7) | 0.0084 (6) | 0.0058 (6) | 0.0130 (6) |
N3 | 0.0400 (8) | 0.0270 (7) | 0.0296 (7) | 0.0077 (6) | −0.0010 (6) | 0.0022 (5) |
N4 | 0.0454 (8) | 0.0309 (7) | 0.0394 (8) | 0.0186 (7) | −0.0039 (6) | 0.0021 (6) |
N5 | 0.0328 (8) | 0.0511 (9) | 0.0477 (9) | 0.0072 (7) | 0.0066 (7) | 0.0133 (7) |
N6 | 0.0311 (8) | 0.0449 (9) | 0.0506 (9) | 0.0104 (7) | 0.0004 (7) | 0.0006 (7) |
O1 | 0.0457 (8) | 0.0363 (7) | 0.0462 (7) | 0.0183 (6) | 0.0058 (6) | −0.0035 (6) |
O2 | 0.0381 (7) | 0.0374 (7) | 0.0547 (8) | 0.0121 (6) | 0.0021 (6) | −0.0073 (6) |
O3 | 0.0342 (7) | 0.0901 (11) | 0.0368 (8) | 0.0044 (8) | 0.0056 (6) | 0.0191 (7) |
O4 | 0.0542 (8) | 0.0436 (7) | 0.0440 (8) | 0.0244 (7) | 0.0067 (7) | 0.0002 (6) |
C1 | 0.0324 (8) | 0.0349 (8) | 0.0328 (8) | 0.0110 (7) | 0.0052 (7) | 0.0097 (7) |
C2 | 0.0388 (9) | 0.0250 (8) | 0.0304 (8) | 0.0077 (7) | 0.0041 (7) | 0.0042 (6) |
C3 | 0.0420 (9) | 0.0327 (8) | 0.0326 (8) | 0.0183 (7) | 0.0015 (7) | −0.0006 (7) |
C4 | 0.0496 (10) | 0.0399 (9) | 0.0285 (8) | 0.0167 (8) | 0.0074 (7) | 0.0074 (7) |
C5 | 0.0515 (11) | 0.0259 (8) | 0.0422 (10) | 0.0080 (8) | −0.0056 (8) | 0.0093 (7) |
C6 | 0.0377 (9) | 0.0390 (9) | 0.0410 (9) | 0.0142 (8) | −0.0046 (7) | 0.0036 (7) |
C7 | 0.0353 (9) | 0.0420 (9) | 0.0285 (8) | 0.0170 (8) | 0.0090 (7) | 0.0083 (7) |
C8 | 0.0336 (9) | 0.0289 (8) | 0.0368 (9) | 0.0132 (7) | 0.0092 (7) | 0.0052 (7) |
Geometric parameters (Å, º) top
Mn1—N5i | 2.1341 (15) | N4—C3 | 1.473 (2) |
Mn1—N5 | 2.1341 (15) | N4—C6 | 1.476 (2) |
Mn1—O1i | 2.1866 (12) | N5—C7 | 1.151 (2) |
Mn1—O1 | 2.1866 (12) | N6—C8 | 1.149 (2) |
Mn1—N1 | 2.4213 (13) | O1—H1OA | 0.818 (5) |
Mn1—N1i | 2.4213 (13) | O1—H1OB | 0.818 (5) |
Mn2—O3 | 2.1616 (13) | O2—H2OA | 0.823 (5) |
Mn2—O3ii | 2.1616 (13) | O2—H2OB | 0.822 (5) |
Mn2—N6ii | 2.1886 (15) | O3—H3OA | 0.815 (5) |
Mn2—N6 | 2.1886 (15) | O3—H3OB | 0.816 (5) |
Mn2—O2ii | 2.2132 (13) | O4—H4OA | 0.819 (5) |
Mn2—O2 | 2.2132 (13) | O4—H4OB | 0.818 (5) |
S1—C7 | 1.6244 (17) | C1—H1A | 0.97 |
S2—C8 | 1.6324 (17) | C1—H1B | 0.97 |
N1—C3 | 1.479 (2) | C2—H2A | 0.97 |
N1—C1 | 1.482 (2) | C2—H2B | 0.97 |
N1—C2 | 1.4871 (19) | C3—H3A | 0.97 |
N2—C5 | 1.468 (2) | C3—H3B | 0.97 |
N2—C4 | 1.470 (2) | C4—H4A | 0.97 |
N2—C1 | 1.472 (2) | C4—H4B | 0.97 |
N3—C4 | 1.473 (2) | C5—H5A | 0.97 |
N3—C2 | 1.474 (2) | C5—H5B | 0.97 |
N3—C6 | 1.475 (2) | C6—H6A | 0.97 |
N4—C5 | 1.471 (2) | C6—H6B | 0.97 |
| | | |
N5i—Mn1—N5 | 180.0 | Mn1—O1—H1OB | 122.8 (16) |
N5i—Mn1—O1i | 90.22 (6) | H1OA—O1—H1OB | 112.3 (13) |
N5—Mn1—O1i | 89.78 (6) | Mn2—O2—H2OA | 117.3 (17) |
N5i—Mn1—O1 | 89.78 (6) | Mn2—O2—H2OB | 113.5 (17) |
N5—Mn1—O1 | 90.22 (6) | H2OA—O2—H2OB | 110.5 (13) |
O1i—Mn1—O1 | 180.00 (6) | Mn2—O3—H3OA | 121.6 (14) |
N5i—Mn1—N1 | 91.80 (5) | Mn2—O3—H3OB | 123.9 (14) |
N5—Mn1—N1 | 88.20 (5) | H3OA—O3—H3OB | 113.8 (13) |
O1i—Mn1—N1 | 88.28 (5) | H4OA—O4—H4OB | 111.5 (13) |
O1—Mn1—N1 | 91.72 (5) | N2—C1—N1 | 112.23 (13) |
N5i—Mn1—N1i | 88.20 (5) | N2—C1—H1A | 109.2 |
N5—Mn1—N1i | 91.80 (5) | N1—C1—H1A | 109.2 |
O1i—Mn1—N1i | 91.72 (5) | N2—C1—H1B | 109.2 |
O1—Mn1—N1i | 88.28 (5) | N1—C1—H1B | 109.2 |
N1—Mn1—N1i | 180.0 | H1A—C1—H1B | 107.9 |
O3—Mn2—O3ii | 180.000 (1) | N3—C2—N1 | 112.10 (12) |
O3—Mn2—N6ii | 91.79 (6) | N3—C2—H2A | 109.2 |
O3ii—Mn2—N6ii | 88.21 (6) | N1—C2—H2A | 109.2 |
O3—Mn2—N6 | 88.21 (6) | N3—C2—H2B | 109.2 |
O3ii—Mn2—N6 | 91.79 (6) | N1—C2—H2B | 109.2 |
N6ii—Mn2—N6 | 180.00 (9) | H2A—C2—H2B | 107.9 |
O3—Mn2—O2ii | 89.78 (6) | N4—C3—N1 | 112.35 (13) |
O3ii—Mn2—O2ii | 90.22 (6) | N4—C3—H3A | 109.1 |
N6ii—Mn2—O2ii | 91.64 (5) | N1—C3—H3A | 109.1 |
N6—Mn2—O2ii | 88.36 (5) | N4—C3—H3B | 109.1 |
O3—Mn2—O2 | 90.22 (6) | N1—C3—H3B | 109.1 |
O3ii—Mn2—O2 | 89.78 (6) | H3A—C3—H3B | 107.9 |
N6ii—Mn2—O2 | 88.36 (5) | N2—C4—N3 | 111.58 (13) |
N6—Mn2—O2 | 91.64 (5) | N2—C4—H4A | 109.3 |
O2ii—Mn2—O2 | 180.0 | N3—C4—H4A | 109.3 |
C3—N1—C1 | 107.72 (12) | N2—C4—H4B | 109.3 |
C3—N1—C2 | 107.55 (12) | N3—C4—H4B | 109.3 |
C1—N1—C2 | 107.60 (12) | H4A—C4—H4B | 108.0 |
C3—N1—Mn1 | 110.08 (9) | N2—C5—N4 | 112.13 (13) |
C1—N1—Mn1 | 112.35 (9) | N2—C5—H5A | 109.2 |
C2—N1—Mn1 | 111.33 (9) | N4—C5—H5A | 109.2 |
C5—N2—C4 | 107.96 (14) | N2—C5—H5B | 109.2 |
C5—N2—C1 | 108.65 (13) | N4—C5—H5B | 109.2 |
C4—N2—C1 | 108.52 (12) | H5A—C5—H5B | 107.9 |
C4—N3—C2 | 108.35 (13) | N3—C6—N4 | 111.32 (13) |
C4—N3—C6 | 108.71 (13) | N3—C6—H6A | 109.4 |
C2—N3—C6 | 108.43 (13) | N4—C6—H6A | 109.4 |
C5—N4—C3 | 108.69 (13) | N3—C6—H6B | 109.4 |
C5—N4—C6 | 107.74 (14) | N4—C6—H6B | 109.4 |
C3—N4—C6 | 108.49 (13) | H6A—C6—H6B | 108.0 |
C7—N5—Mn1 | 160.59 (15) | N5—C7—S1 | 179.83 (19) |
C8—N6—Mn2 | 177.51 (15) | N6—C8—S2 | 178.40 (16) |
Mn1—O1—H1OA | 124.3 (15) | | |
| | | |
N5—Mn1—N1—C3 | 71.47 (10) | C6—N3—C2—N1 | −59.01 (17) |
N5i—Mn1—N1—C3 | −108.53 (10) | C3—N1—C2—N3 | 57.98 (17) |
O1—Mn1—N1—C3 | −18.70 (10) | C1—N1—C2—N3 | −57.83 (17) |
O1i—Mn1—N1—C3 | 161.30 (10) | Mn1—N1—C2—N3 | 178.66 (10) |
N5—Mn1—N1—C1 | −168.48 (11) | C5—N4—C3—N1 | −57.98 (17) |
N5i—Mn1—N1—C1 | 11.52 (11) | C6—N4—C3—N1 | 58.90 (18) |
O1—Mn1—N1—C1 | 101.36 (10) | C1—N1—C3—N4 | 57.78 (16) |
O1i—Mn1—N1—C1 | −78.64 (10) | C2—N1—C3—N4 | −57.94 (16) |
N5—Mn1—N1—C2 | −47.71 (11) | Mn1—N1—C3—N4 | −179.40 (10) |
N5i—Mn1—N1—C2 | 132.29 (11) | C5—N2—C4—N3 | −58.58 (17) |
O1—Mn1—N1—C2 | −137.88 (10) | C1—N2—C4—N3 | 59.01 (18) |
O1i—Mn1—N1—C2 | 42.12 (10) | C2—N3—C4—N2 | −59.06 (17) |
O1—Mn1—N5—C7 | 167.5 (4) | C6—N3—C4—N2 | 58.59 (17) |
O1i—Mn1—N5—C7 | −12.5 (4) | C4—N2—C5—N4 | 59.58 (17) |
N1i—Mn1—N5—C7 | −104.2 (4) | C1—N2—C5—N4 | −57.93 (17) |
N1—Mn1—N5—C7 | 75.8 (4) | C3—N4—C5—N2 | 57.73 (17) |
C5—N2—C1—N1 | 58.35 (17) | C6—N4—C5—N2 | −59.63 (17) |
C4—N2—C1—N1 | −58.80 (17) | C4—N3—C6—N4 | −58.62 (17) |
C3—N1—C1—N2 | −57.94 (16) | C2—N3—C6—N4 | 58.98 (17) |
C2—N1—C1—N2 | 57.75 (16) | C5—N4—C6—N3 | 58.67 (17) |
Mn1—N1—C1—N2 | −179.36 (10) | C3—N4—C6—N3 | −58.82 (18) |
C4—N3—C2—N1 | 58.82 (17) | | |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y−1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4OB···S1iii | 0.82 (1) | 2.63 (1) | 3.3533 (16) | 148 (2) |
O2—H2OB···S2iv | 0.82 (1) | 2.54 (1) | 3.2949 (15) | 154 (2) |
O4—H4OA···N4 | 0.82 (1) | 2.00 (1) | 2.817 (2) | 174 (3) |
O2—H2OA···N3 | 0.82 (1) | 1.99 (1) | 2.8055 (19) | 170 (2) |
O3—H3OB···O4v | 0.82 (1) | 2.00 (1) | 2.797 (2) | 166 (2) |
O3—H3OA···N2vi | 0.82 (1) | 2.04 (1) | 2.843 (2) | 169 (2) |
O1—H1OA···O4vii | 0.82 (1) | 1.93 (1) | 2.7424 (19) | 176 (2) |
Symmetry codes: (iii) −x, −y, −z+1; (iv) x−1, y, z; (v) −x, −y, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Mn(NCS)2(C6H12N4)2(H2O)2]·[Mn(NCS)2(H2O)4]·2H2O |
Mr | 766.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 288 |
a, b, c (Å) | 7.969 (1), 9.111 (1), 13.076 (2) |
α, β, γ (°) | 94.34 (1), 96.83 (1), 115.16 (1) |
V (Å3) | 844.76 (19) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.48 × 0.48 × 0.40 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1994) |
Tmin, Tmax | 0.615, 0.653 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3694, 3316, 2853 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.062, 1.06 |
No. of reflections | 3316 |
No. of parameters | 226 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.27 |
Selected geometric parameters (Å, º) topMn1—N5 | 2.1341 (15) | Mn2—O3 | 2.1616 (13) |
Mn1—O1 | 2.1866 (12) | Mn2—N6 | 2.1886 (15) |
Mn1—N1 | 2.4213 (13) | Mn2—O2 | 2.2132 (13) |
| | | |
N5—Mn1—O1 | 90.22 (6) | O3—Mn2—N6ii | 91.79 (6) |
N5—Mn1—N1 | 88.20 (5) | O3—Mn2—O2 | 90.22 (6) |
N5i—Mn1—N1i | 88.20 (5) | N6—Mn2—O2 | 91.64 (5) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y−1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4OB···S1iii | 0.818 (5) | 2.631 (14) | 3.3533 (16) | 148 (2) |
O2—H2OB···S2iv | 0.822 (5) | 2.536 (11) | 3.2949 (15) | 154 (2) |
O4—H4OA···N4 | 0.819 (5) | 2.001 (6) | 2.817 (2) | 174 (3) |
O2—H2OA···N3 | 0.823 (5) | 1.992 (7) | 2.8055 (19) | 170 (2) |
O3—H3OB···O4v | 0.816 (5) | 1.998 (7) | 2.797 (2) | 166 (2) |
O3—H3OA···N2vi | 0.815 (5) | 2.040 (7) | 2.843 (2) | 168.5 (19) |
O1—H1OA···O4vii | 0.818 (5) | 1.925 (6) | 2.7424 (19) | 176 (2) |
Symmetry codes: (iii) −x, −y, −z+1; (iv) x−1, y, z; (v) −x, −y, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z+1. |
Metal complexes that assemble into specific supramolecular structures in the crystal lattice have generated considerable interest because of their potential use in developing new materials with magnetic, optical and catalytic properties (Lehn, 1990). Materials with multidimensional supramolecular architectures have been organized by coordinate, covalent or hydrogen bonding (Gemma & Jonathan, 1999). The vast majority of current work centers around the controlled assembly of donor and acceptor building blocks (particularly involving hydrogen-bond acid–base pairs, e.g. nucleobase) in order to generate an entirely supramolecular polymer, i.e. a material held together solely by non-covalent interactions. With this in mind, considering hexamethylenetetramine (hmt) as a potential tetradentate ligand or hydrogen-bond acceptor, and suitable for the self-assembly of supramolecular architectures (Stuart et al., 1998), we sought to synthesize a multidimensional supramolecular compound containing it. Herein we report the three-dimensional supramolecular architecture of [Mn(hmt)2(H2O)2(NCS)2]·[Mn(H2O)4(NCS)2]·2H2O, (I).
The molecular structure of (I) is shown in Fig. 1. The geometry around Mn1 is octahedral; the two O atoms of the coordinated water molecules and the two N atoms from two NCS- define the equatorial positions, whereas an N atom from each of the hmt ligands occupies the axial ones. The axial Mn1—N1 bond distance of 2.4213 (13) Å is significantly longer than the equatorial Mn1—O1 bonds of 2.1865 (12) Å and the Mn1—N5 bonds of 2.1342 (15) Å. Mn2 is also in an octahedral environment. The coordination polyhedron is formed by two NCS- and four water molecules, elongated along the axis defined by the water molecules; the axial Mn2—O2 distance is 2.2132 (13) Å. Both Mn1- and Mn2-containing species are located on inversion centres. In Fig. 2, both the interlayer Mn1···Mn1 and Mn2···Mn2 distances are 7.969 Å, the distance of Mn1···Mn1 between adjacent chains is 9.280 Å in the same layer, the shortest intermolecular Mn1···Mn2 distance is 7.296 Å and the shorter intermolecular Mn1···Mn2 distance is 8.640 Å. The independent moieties [Mn(hmt)2(H2O)2(NCS)2] and [Mn(H2O)4(NCS)2] are connected by four hydrogen bonds (Table 2) to form a two-dimensional structure. Adjacent two-dimensional chains are connected by further hydrogen bonds to form a three-dimensional supramolecular architecture.