Tuning of crystallization method and ligand con­formation to give a mononuclear com­pound or two-dimensional SCO coordination polymer based on a new semi-rigid V-shaped bis-pyridyl bis-amide ligand

With the new semi-rigid V-shaped bidentate pyridyl amide com­pound 5-methyl-N,N′-bis­(pyridin-4-yl)benzene-1,3-dicarboxamide (L) as an auxiliary ligand and the Fe^II ion as the metal centre, one mononuclear com­plex, bis­(methanol-κO)bis­[5-methyl-N,N′-bis­(pyridin-4-yl)benzene-1,3-dicarboxamide-κN]bis­(thio­cyanato-κN)iron(II), [Fe(SCN)₂(C₁₉H₁₆N₄O₂)₂(CH₃OH)₂] (1), and one two-dimensional coordination polymer, catena-poly[[[bis­(thio­cyanato-κN)iron(II)]-bis­[μ-5-methyl-N,N′-bis­(pyridin-4-yl)benzene-1,3-dicarboxamide-κ²N:N′]] methanol disolvate dihydrate], {[Fe(SCN)₂(C₁₉H₁₆N₄O₂)₂]·2CH₃OH·2H₂O}_n (2), were prepared by slow evaporation and H-tube diffusion methods, respectively, indicating the effect of the method of crystallization on the structure type of the target product. Both com­plexes have been structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray crystallography. The single-crystal X-ray diffraction analysis shows that L functions as a monodentate ligand in mononuclear 1, while it coordinates in a bidentate manner to two inde­­pendent Fe(SCN)₂ units in com­plex 2, with a different conformation from that in 1 and the ligands point in two almost orthogonal directions, therefore leading to a two-dimensional grid-like network. Investigation of the magnetic properties reveals the always high-spin state of the Fe^II centre over the whole temperature range in 1 and a gradual thermally-induced incom­plete spin crossover (SCO) behaviour below 150 K in 2, demonstrating the influence of the different coordination fields on the spin properties of the metal ions. The current results provide useful information for the rational design of functional com­plexes with different structure dimensionalities by employing different conformations of the ligand and different crystallization methods.

Computing details

For both structures, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Bis(methanol-κO)bis[5-methyl-N,N'-bis(pyridin-4-yl)benzene-1,3-dicarboxamide-κN]bis(thiocyanato-κN)iron(II) (mono)

Crystal data

[Fe(SCN)2(C19H16N4O2)2(CH4O)2]	Z = 1
Mr = 900.81	F(000) = 468
Triclinic, P1	Dx = 1.496 Mg m^−3
a = 9.0061 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3811 (8) Å	Cell parameters from 2433 reflections
c = 11.6830 (9) Å	θ = 2.9–28.9°
α = 82.848 (7)°	µ = 0.55 mm^−1
β = 84.322 (7)°	T = 293 K
γ = 67.522 (8)°	Block, pale-yellow
V = 999.87 (15) Å^3	0.15 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2889 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
φ and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan	h = −10→10
Tmin = 0.851, Tmax = 1.000	k = −12→10
6227 measured reflections	l = −13→13
3530 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0511P)^2 + 0.4901P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3530 reflections	Δρmax = 0.47 e Å^−3
277 parameters	Δρmin = −0.30 e Å^−3

Special details

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. Single crystals of complexes 1 and 2 for X-ray diffraction analysis with suitable dimensions were mounted on a glass rod, and the crystal data were collected on a Bruker APEX2 CCD diffractometer with a Mo Kα sealed tube (λ = 0.71073 Å), using the ω scan mode. The data for complex 1 was collected at room temperature, while that for complex 2 was collected at 130 K. The structures were solved using the direct method and expanded using Fourier difference techniques with the SHELXTL-2018 program package (Sheldrick, 2015). The non-hydrogen atoms were refined anisotropically with anisotropic displacement coefficients.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.000000	0.000000	0.000000	0.03167 (17)
S1	0.27502 (11)	−0.45716 (8)	0.18595 (7)	0.0496 (2)
O1	−0.2451 (2)	0.07940 (18)	0.06982 (16)	0.0404 (5)
H1A	−0.283089	0.024000	0.109999	0.048*
O2	0.0801 (3)	0.2137 (2)	0.55904 (17)	0.0587 (6)
O3	0.3961 (4)	0.7426 (3)	0.58814 (19)	0.0774 (9)
N1	0.0508 (3)	−0.1976 (2)	0.1020 (2)	0.0416 (6)
N2	0.0686 (3)	0.0801 (2)	0.14304 (18)	0.0341 (5)
N3	0.1774 (3)	0.2877 (2)	0.38949 (19)	0.0389 (6)
H3A	0.228006	0.340317	0.359540	0.047*
N4	0.3479 (3)	0.7185 (2)	0.40763 (19)	0.0377 (5)
H4	0.299301	0.682395	0.369185	0.045*
N5	0.5832 (3)	0.9527 (2)	0.2021 (2)	0.0478 (6)
C1	0.1411 (4)	−0.3058 (3)	0.1376 (2)	0.0384 (7)
C2	0.0295 (3)	0.0583 (3)	0.2549 (2)	0.0367 (6)
H2	−0.023892	−0.002910	0.275617	0.044*
C3	0.0625 (3)	0.1200 (3)	0.3422 (2)	0.0356 (6)
H3	0.031911	0.100970	0.418776	0.043*
C4	0.1427 (3)	0.2111 (2)	0.3125 (2)	0.0316 (6)
C5	0.1891 (3)	0.2295 (3)	0.1969 (2)	0.0408 (7)
H5	0.246689	0.286873	0.173699	0.049*
C6	0.1506 (3)	0.1639 (3)	0.1171 (2)	0.0400 (7)
H6	0.183415	0.178384	0.040159	0.048*
C7	0.1416 (3)	0.2901 (3)	0.5054 (2)	0.0345 (6)
C8	0.1815 (3)	0.3924 (3)	0.5650 (2)	0.0298 (6)
C9	0.1582 (3)	0.3836 (3)	0.6842 (2)	0.0317 (6)
H9	0.116079	0.319321	0.721096	0.038*
C10	0.1960 (3)	0.4676 (3)	0.7496 (2)	0.0341 (6)
C11	0.1728 (4)	0.4559 (3)	0.8799 (2)	0.0523 (8)
H11A	0.123431	0.389079	0.904519	0.079*
H11B	0.104783	0.545514	0.904676	0.079*
H11C	0.275361	0.425513	0.913092	0.079*
C12	0.2577 (3)	0.5628 (3)	0.6923 (2)	0.0359 (6)
H12	0.285875	0.618701	0.735330	0.043*
C13	0.2787 (3)	0.5775 (3)	0.5732 (2)	0.0323 (6)
C14	0.2412 (3)	0.4909 (3)	0.5090 (2)	0.0321 (6)
H14	0.255909	0.498583	0.428844	0.039*
C15	0.3448 (3)	0.6869 (3)	0.5243 (2)	0.0406 (7)
C16	0.4216 (3)	0.8037 (3)	0.3431 (2)	0.0366 (6)
C17	0.4890 (3)	0.8844 (3)	0.3901 (3)	0.0443 (7)
H17	0.480719	0.890813	0.469300	0.053*
C18	0.5680 (4)	0.9543 (3)	0.3165 (3)	0.0468 (7)
H18	0.614069	1.006529	0.348962	0.056*
C19	0.5109 (4)	0.8810 (3)	0.1578 (3)	0.0509 (8)
H19	0.514405	0.881872	0.077944	0.061*
C20	0.4318 (4)	0.8061 (3)	0.2243 (3)	0.0477 (7)
H20	0.384661	0.756725	0.189130	0.057*
C21	−0.3411 (4)	0.2203 (3)	0.0934 (3)	0.0598 (9)
H21A	−0.274332	0.274467	0.086179	0.090*
H21B	−0.389242	0.220575	0.170468	0.090*
H21C	−0.424077	0.260394	0.039252	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0437 (3)	0.0343 (3)	0.0252 (3)	−0.0241 (3)	−0.0004 (2)	−0.0031 (2)
S1	0.0743 (6)	0.0378 (4)	0.0416 (5)	−0.0275 (4)	−0.0082 (4)	0.0030 (3)
O1	0.0477 (11)	0.0408 (10)	0.0401 (11)	−0.0268 (9)	0.0094 (9)	−0.0066 (9)
O2	0.1046 (18)	0.0709 (14)	0.0314 (11)	−0.0681 (15)	−0.0087 (11)	0.0025 (10)
O3	0.141 (2)	0.1020 (19)	0.0393 (13)	−0.1011 (19)	0.0178 (14)	−0.0242 (13)
N1	0.0565 (16)	0.0399 (14)	0.0366 (14)	−0.0287 (13)	−0.0039 (12)	0.0028 (11)
N2	0.0420 (13)	0.0365 (12)	0.0293 (12)	−0.0206 (10)	−0.0008 (10)	−0.0046 (9)
N3	0.0552 (15)	0.0436 (13)	0.0324 (13)	−0.0340 (12)	0.0041 (11)	−0.0110 (10)
N4	0.0452 (14)	0.0424 (12)	0.0364 (13)	−0.0293 (11)	−0.0027 (11)	−0.0007 (10)
N5	0.0484 (15)	0.0451 (14)	0.0565 (17)	−0.0278 (12)	0.0015 (12)	0.0020 (12)
C1	0.0586 (19)	0.0483 (17)	0.0246 (14)	−0.0389 (16)	0.0035 (13)	−0.0049 (13)
C2	0.0418 (16)	0.0379 (14)	0.0392 (16)	−0.0245 (13)	−0.0007 (12)	−0.0052 (12)
C3	0.0470 (16)	0.0378 (14)	0.0284 (14)	−0.0234 (13)	−0.0014 (12)	−0.0031 (11)
C4	0.0358 (14)	0.0296 (13)	0.0328 (15)	−0.0142 (11)	−0.0036 (11)	−0.0074 (11)
C5	0.0535 (18)	0.0437 (15)	0.0389 (16)	−0.0334 (14)	0.0075 (14)	−0.0114 (13)
C6	0.0556 (18)	0.0455 (16)	0.0301 (15)	−0.0317 (14)	0.0044 (13)	−0.0083 (12)
C7	0.0410 (15)	0.0349 (14)	0.0326 (15)	−0.0190 (12)	−0.0061 (12)	−0.0024 (11)
C8	0.0312 (13)	0.0325 (13)	0.0279 (14)	−0.0137 (11)	−0.0027 (11)	−0.0042 (11)
C9	0.0365 (14)	0.0305 (13)	0.0293 (14)	−0.0151 (11)	0.0000 (11)	−0.0001 (11)
C10	0.0409 (15)	0.0357 (14)	0.0257 (14)	−0.0148 (12)	0.0000 (12)	−0.0037 (11)
C11	0.084 (2)	0.0535 (18)	0.0295 (16)	−0.0364 (18)	0.0030 (15)	−0.0083 (14)
C12	0.0447 (16)	0.0388 (14)	0.0300 (15)	−0.0203 (13)	0.0011 (12)	−0.0113 (12)
C13	0.0366 (14)	0.0339 (13)	0.0287 (14)	−0.0163 (12)	0.0022 (11)	−0.0050 (11)
C14	0.0415 (15)	0.0366 (14)	0.0224 (13)	−0.0195 (12)	−0.0016 (11)	−0.0020 (11)
C15	0.0495 (17)	0.0427 (15)	0.0388 (16)	−0.0278 (14)	0.0110 (13)	−0.0130 (13)
C16	0.0338 (15)	0.0357 (14)	0.0419 (16)	−0.0166 (12)	0.0008 (12)	0.0004 (12)
C17	0.0488 (17)	0.0433 (16)	0.0479 (18)	−0.0257 (14)	0.0049 (14)	−0.0085 (13)
C18	0.0512 (18)	0.0431 (16)	0.056 (2)	−0.0290 (15)	0.0024 (15)	−0.0069 (14)
C19	0.058 (2)	0.0611 (19)	0.0421 (18)	−0.0351 (17)	−0.0044 (15)	0.0071 (15)
C20	0.0552 (19)	0.0580 (18)	0.0435 (18)	−0.0376 (16)	−0.0088 (14)	0.0039 (14)
C21	0.074 (2)	0.0573 (19)	0.054 (2)	−0.0327 (18)	0.0127 (18)	−0.0127 (16)

Geometric parameters (Å, º)

Fe1—N1^i	2.150 (2)	C5—H5	0.9300
Fe1—N1	2.150 (2)	C6—H6	0.9300
Fe1—O1^i	2.1535 (18)	C7—C8	1.506 (3)
Fe1—O1	2.1535 (18)	C8—C9	1.384 (3)
Fe1—N2^i	2.193 (2)	C8—C14	1.395 (3)
Fe1—N2	2.193 (2)	C9—C10	1.381 (3)
S1—C1	1.645 (3)	C9—H9	0.9300
O1—C21	1.431 (4)	C10—C12	1.383 (3)
O1—H1A	0.8482	C10—C11	1.511 (4)
O2—C7	1.213 (3)	C11—H11A	0.9600
O3—C15	1.218 (3)	C11—H11B	0.9600
N1—C1	1.161 (4)	C11—H11C	0.9600
N2—C6	1.332 (3)	C12—C13	1.384 (4)
N2—C2	1.334 (3)	C12—H12	0.9300
N3—C7	1.361 (3)	C13—C14	1.392 (3)
N3—C4	1.401 (3)	C13—C15	1.502 (3)
N3—H3A	0.8600	C14—H14	0.9300
N4—C15	1.361 (3)	C16—C20	1.380 (4)
N4—C16	1.406 (3)	C16—C17	1.392 (4)
N4—H4	0.8600	C17—C18	1.375 (4)
N5—C18	1.331 (4)	C17—H17	0.9300
N5—C19	1.333 (4)	C18—H18	0.9300
C2—C3	1.381 (4)	C19—C20	1.371 (4)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.389 (3)	C20—H20	0.9300
C3—H3	0.9300	C21—H21A	0.9600
C4—C5	1.386 (4)	C21—H21B	0.9600
C5—C6	1.363 (4)	C21—H21C	0.9600
N1^i—Fe1—N1	180.0	C9—C8—C14	119.3 (2)
N1^i—Fe1—O1^i	92.01 (8)	C9—C8—C7	115.9 (2)
N1—Fe1—O1^i	87.99 (8)	C14—C8—C7	124.7 (2)
N1^i—Fe1—O1	87.99 (8)	C10—C9—C8	121.8 (2)
N1—Fe1—O1	92.01 (8)	C10—C9—H9	119.1
O1^i—Fe1—O1	180.0	C8—C9—H9	119.1
N1^i—Fe1—N2^i	89.09 (8)	C9—C10—C12	117.9 (2)
N1—Fe1—N2^i	90.92 (8)	C9—C10—C11	121.5 (2)
O1^i—Fe1—N2^i	88.57 (7)	C12—C10—C11	120.6 (2)
O1—Fe1—N2^i	91.43 (7)	C10—C11—H11A	109.5
N1^i—Fe1—N2	90.92 (8)	C10—C11—H11B	109.5
N1—Fe1—N2	89.08 (8)	H11A—C11—H11B	109.5
O1^i—Fe1—N2	91.43 (7)	C10—C11—H11C	109.5
O1—Fe1—N2	88.57 (7)	H11A—C11—H11C	109.5
N2^i—Fe1—N2	180.0	H11B—C11—H11C	109.5
C21—O1—Fe1	127.55 (17)	C10—C12—C13	122.2 (2)
C21—O1—H1A	109.3	C10—C12—H12	118.9
Fe1—O1—H1A	119.6	C13—C12—H12	118.9
C1—N1—Fe1	150.8 (2)	C12—C13—C14	118.9 (2)
C6—N2—C2	116.0 (2)	C12—C13—C15	115.6 (2)
C6—N2—Fe1	117.87 (17)	C14—C13—C15	125.4 (2)
C2—N2—Fe1	126.06 (16)	C13—C14—C8	119.9 (2)
C7—N3—C4	128.7 (2)	C13—C14—H14	120.1
C7—N3—H3A	115.7	C8—C14—H14	120.1
C4—N3—H3A	115.7	O3—C15—N4	122.0 (2)
C15—N4—C16	127.2 (2)	O3—C15—C13	120.1 (3)
C15—N4—H4	116.4	N4—C15—C13	117.9 (2)
C16—N4—H4	116.4	C20—C16—C17	117.0 (2)
C18—N5—C19	116.2 (2)	C20—C16—N4	118.1 (2)
N1—C1—S1	177.7 (2)	C17—C16—N4	124.9 (3)
N2—C2—C3	124.7 (2)	C18—C17—C16	118.4 (3)
N2—C2—H2	117.7	C18—C17—H17	120.8
C3—C2—H2	117.7	C16—C17—H17	120.8
C2—C3—C4	118.2 (2)	N5—C18—C17	124.8 (3)
C2—C3—H3	120.9	N5—C18—H18	117.6
C4—C3—H3	120.9	C17—C18—H18	117.6
C5—C4—C3	117.1 (2)	N5—C19—C20	123.3 (3)
C5—C4—N3	117.6 (2)	N5—C19—H19	118.4
C3—C4—N3	125.3 (2)	C20—C19—H19	118.4
C6—C5—C4	120.2 (2)	C19—C20—C16	120.3 (3)
C6—C5—H5	119.9	C19—C20—H20	119.9
C4—C5—H5	119.9	C16—C20—H20	119.9
N2—C6—C5	123.7 (2)	O1—C21—H21A	109.4
N2—C6—H6	118.2	O1—C21—H21B	109.5
C5—C6—H6	118.2	H21A—C21—H21B	109.5
O2—C7—N3	122.0 (2)	O1—C21—H21C	109.5
O2—C7—C8	121.0 (2)	H21A—C21—H21C	109.5
N3—C7—C8	117.1 (2)	H21B—C21—H21C	109.5
C6—N2—C2—C3	2.6 (4)	C11—C10—C12—C13	−179.2 (3)
Fe1—N2—C2—C3	−174.1 (2)	C10—C12—C13—C14	−2.0 (4)
N2—C2—C3—C4	−0.2 (4)	C10—C12—C13—C15	179.2 (3)
C2—C3—C4—C5	−2.3 (4)	C12—C13—C14—C8	0.8 (4)
C2—C3—C4—N3	176.3 (2)	C15—C13—C14—C8	179.5 (3)
C7—N3—C4—C5	178.5 (3)	C9—C8—C14—C13	0.9 (4)
C7—N3—C4—C3	−0.1 (5)	C7—C8—C14—C13	−178.0 (2)
C3—C4—C5—C6	2.4 (4)	C16—N4—C15—O3	7.1 (5)
N3—C4—C5—C6	−176.3 (3)	C16—N4—C15—C13	−171.6 (2)
C2—N2—C6—C5	−2.4 (4)	C12—C13—C15—O3	9.8 (4)
Fe1—N2—C6—C5	174.5 (2)	C14—C13—C15—O3	−169.0 (3)
C4—C5—C6—N2	0.0 (5)	C12—C13—C15—N4	−171.5 (2)
C4—N3—C7—O2	5.0 (5)	C14—C13—C15—N4	9.7 (4)
C4—N3—C7—C8	−174.9 (2)	C15—N4—C16—C20	170.5 (3)
O2—C7—C8—C9	6.0 (4)	C15—N4—C16—C17	−8.0 (4)
N3—C7—C8—C9	−174.1 (2)	C20—C16—C17—C18	−3.5 (4)
O2—C7—C8—C14	−175.1 (3)	N4—C16—C17—C18	175.1 (3)
N3—C7—C8—C14	4.8 (4)	C19—N5—C18—C17	2.3 (5)
C14—C8—C9—C10	−1.5 (4)	C16—C17—C18—N5	1.1 (5)
C7—C8—C9—C10	177.5 (2)	C18—N5—C19—C20	−3.4 (5)
C8—C9—C10—C12	0.3 (4)	N5—C19—C20—C16	1.0 (5)
C8—C9—C10—C11	−179.0 (3)	C17—C16—C20—C19	2.5 (4)
C9—C10—C12—C13	1.4 (4)	N4—C16—C20—C19	−176.1 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···S1^ii	0.93	2.76	3.612 (3)	153
C17—H17···O3	0.93	2.24	2.816 (4)	119
C5—H5···S1^ii	0.93	2.79	3.605 (3)	147
C3—H3···O2	0.93	2.29	2.864 (3)	119
N4—H4···S1^ii	0.86	2.80	3.590 (2)	154
O1—H1A···N5^iii	0.85	1.84	2.662 (3)	163
N4—H4···S1^ii	0.86	2.80	3.590 (2)	154
C3—H3···O2	0.93	2.29	2.864 (3)	119
C5—H5···S1^ii	0.93	2.79	3.605 (3)	147
C17—H17···O3	0.93	2.24	2.816 (4)	119
C20—H20···S1^ii	0.93	2.76	3.612 (3)	153
O1—H1A···N5^iii	0.85	1.84	2.662 (3)	163
O1—H1A···N5^iii	0.85	1.84	2.662 (3)	163
N4—H4···S1^ii	0.86	2.80	3.590 (2)	154
C3—H3···O2	0.93	2.29	2.864 (3)	119
C5—H5···S1^ii	0.93	2.79	3.605 (3)	147
C17—H17···O3	0.93	2.24	2.816 (4)	119
C20—H20···S1^ii	0.93	2.76	3.612 (3)	153
O1—H1A···N5^iii	0.85	1.84	2.662 (3)	163
N3—H3A···S1^ii	0.86	2.86	3.639 (2)	152
N4—H4···S1^ii	0.86	2.80	3.590 (2)	154
C3—H3···O2	0.93	2.29	2.864 (3)	119
C5—H5···S1^ii	0.93	2.79	3.605 (3)	147
C17—H17···O3	0.93	2.24	2.816 (4)	119
C20—H20···S1^ii	0.93	2.76	3.612 (3)	153

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

catena-Poly[[[bis(thiocyanato-κN)iron(II)]-bis[µ-5-methyl-N,N'-bis(pyridin-4-yl)benzene-1,3-dicarboxamide-κ²N:N']] methanol disolvate dihydrate] (2D)

Crystal data

[Fe(SCN)2(C19H16N4O2)2]·2CH4O·2H2O	F(000) = 976
Mr = 936.84	Dx = 1.434 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3685 (5) Å	Cell parameters from 3211 reflections
b = 17.9701 (10) Å	θ = 3.0–29.1°
c = 14.8291 (11) Å	µ = 0.51 mm^−1
β = 103.411 (7)°	T = 130 K
V = 2169.2 (2) Å^3	Block, gold-yellow
Z = 2	0.23 × 0.19 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3115 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
φ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan	h = −8→9
Tmin = 0.782, Tmax = 1.000	k = −20→21
8931 measured reflections	l = −17→17
3811 independent reflections

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.0707P)^2 + 6.4322P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.027
3811 reflections	Δρmax = 2.06 e Å^−3
288 parameters	Δρmin = −1.11 e Å^−3

Special details

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. Single crystals of complexes 1 and 2 for X-ray diffraction analysis with suitable dimensions were mounted on a glass rod, and the crystal data were collected on a Bruker APEX2 CCD diffractometer with a Mo Kα sealed tube (λ = 0.71073 Å), using the ω scan mode. The data for complex 1 was collected at room temperature, while that for complex 2 was collected at 130 K. The structures were solved using the direct method and expanded using Fourier difference techniques with the SHELXTL-2018 program package (Sheldrick, 2015). The non-hydrogen atoms were refined anisotropically with anisotropic displacement coefficients

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe1	−0.500000	0.000000	0.500000	0.0170 (2)
S1	−0.1647 (2)	0.15825 (9)	0.34619 (10)	0.0582 (5)
O1	0.1135 (3)	−0.08237 (14)	0.92755 (19)	0.0256 (6)
O2	0.4002 (4)	0.23954 (16)	1.1060 (2)	0.0322 (7)
O3	0.3237 (5)	0.2284 (2)	0.2799 (3)	0.0602 (11)
H3	0.352785	0.238912	0.230755	0.072*
O4	0.0956 (5)	0.20151 (19)	0.8785 (3)	0.0588 (11)
H4A	−0.006479	0.207578	0.874358	0.071*
H4B	0.140194	0.243200	0.869041	0.071*
N1	−0.3574 (4)	0.06355 (18)	0.4275 (2)	0.0228 (7)
N2	−0.2970 (4)	0.00787 (17)	0.6273 (2)	0.0203 (7)
N3	0.0588 (4)	0.03568 (17)	0.8763 (2)	0.0216 (7)
H3A	0.081400	0.081602	0.889885	0.026*
N4	0.6508 (4)	0.20037 (18)	1.0881 (2)	0.0232 (7)
H4	0.710515	0.161119	1.090788	0.028*
N5	0.8839 (4)	0.39530 (17)	1.0320 (2)	0.0219 (7)
C1	−0.2773 (5)	0.1025 (3)	0.3939 (3)	0.0314 (10)
C2	−0.2043 (5)	0.0688 (2)	0.6473 (3)	0.0271 (9)
H2	−0.220906	0.107129	0.604082	0.033*
C3	−0.0864 (5)	0.0783 (2)	0.7275 (3)	0.0262 (9)
H3B	−0.025966	0.122206	0.737913	0.031*
C4	−0.0577 (5)	0.0218 (2)	0.7933 (3)	0.0205 (8)
C5	−0.1489 (5)	−0.0431 (2)	0.7724 (3)	0.0219 (8)
H5	−0.131070	−0.083268	0.813047	0.026*
C6	−0.2662 (5)	−0.0470 (2)	0.6903 (3)	0.0217 (8)
H6	−0.327925	−0.090346	0.677709	0.026*
C7	0.2700 (5)	0.0135 (2)	1.0168 (2)	0.0198 (8)
C8	0.3102 (5)	0.0886 (2)	1.0295 (3)	0.0215 (8)
H8	0.245924	0.124500	0.992987	0.026*
C9	0.4475 (5)	0.1092 (2)	1.0972 (3)	0.0215 (8)
C10	0.5393 (5)	0.0567 (2)	1.1553 (3)	0.0229 (8)
H10	0.631782	0.071416	1.199601	0.028*
C11	0.4945 (5)	−0.0179 (2)	1.1478 (3)	0.0224 (8)
C12	0.3608 (5)	−0.0388 (2)	1.0775 (3)	0.0212 (8)
H12	0.331172	−0.088707	1.070797	0.025*
C13	0.1400 (4)	−0.0158 (2)	0.9377 (2)	0.0199 (8)
C14	0.4955 (5)	0.1896 (2)	1.0996 (3)	0.0229 (9)
C15	0.7244 (5)	0.2670 (2)	1.0724 (3)	0.0220 (8)
C16	0.6493 (5)	0.3360 (2)	1.0673 (3)	0.0234 (8)
H16	0.543969	0.340760	1.077133	0.028*
C17	0.7324 (5)	0.3971 (2)	1.0475 (3)	0.0239 (8)
H17	0.680218	0.443066	1.044600	0.029*
C18	0.9532 (5)	0.3281 (2)	1.0351 (3)	0.0297 (10)
H18	1.056928	0.324748	1.022724	0.036*
C19	0.8809 (5)	0.2641 (2)	1.0552 (3)	0.0312 (10)
H19	0.935724	0.218850	1.057463	0.037*
C21	0.1677 (8)	0.2512 (5)	0.2908 (5)	0.076 (2)
H21A	0.164110	0.247262	0.354840	0.114*
H21B	0.084547	0.219908	0.254041	0.114*
H21C	0.148499	0.301901	0.270832	0.114*
C20	0.5866 (5)	−0.0743 (2)	1.2144 (3)	0.0300 (10)
H20A	0.692207	−0.054554	1.244374	0.045*
H20B	0.600904	−0.118796	1.181400	0.045*
H20C	0.525760	−0.085582	1.260189	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0180 (4)	0.0137 (4)	0.0189 (4)	0.0019 (3)	0.0032 (3)	−0.0002 (3)
S1	0.0662 (9)	0.0683 (10)	0.0414 (7)	−0.0394 (8)	0.0154 (7)	−0.0018 (7)
O1	0.0259 (15)	0.0176 (14)	0.0296 (15)	−0.0039 (12)	−0.0010 (12)	−0.0003 (11)
O2	0.0322 (17)	0.0246 (16)	0.0441 (18)	−0.0064 (14)	0.0180 (14)	−0.0057 (13)
O3	0.056 (2)	0.062 (3)	0.068 (3)	0.001 (2)	0.025 (2)	0.006 (2)
O4	0.084 (3)	0.0266 (18)	0.056 (2)	0.0053 (19)	−0.004 (2)	0.0004 (16)
N1	0.0253 (17)	0.0195 (17)	0.0238 (17)	0.0002 (15)	0.0065 (14)	0.0022 (14)
N2	0.0205 (16)	0.0159 (16)	0.0238 (17)	0.0013 (13)	0.0042 (13)	0.0015 (13)
N3	0.0248 (17)	0.0155 (16)	0.0221 (17)	−0.0048 (14)	0.0007 (14)	−0.0015 (13)
N4	0.0244 (17)	0.0156 (16)	0.0302 (18)	−0.0047 (14)	0.0072 (14)	0.0009 (13)
N5	0.0243 (17)	0.0167 (16)	0.0245 (17)	−0.0019 (14)	0.0052 (14)	0.0022 (13)
C1	0.031 (2)	0.040 (3)	0.021 (2)	−0.005 (2)	0.0009 (18)	−0.0063 (19)
C2	0.030 (2)	0.021 (2)	0.028 (2)	−0.0043 (18)	0.0016 (17)	0.0062 (17)
C3	0.027 (2)	0.020 (2)	0.029 (2)	−0.0042 (17)	0.0018 (17)	0.0025 (17)
C4	0.0192 (19)	0.0195 (19)	0.0227 (19)	0.0001 (16)	0.0045 (16)	−0.0012 (15)
C5	0.024 (2)	0.0196 (19)	0.022 (2)	−0.0012 (16)	0.0048 (16)	0.0026 (15)
C6	0.0220 (19)	0.0182 (19)	0.023 (2)	−0.0036 (16)	0.0027 (16)	−0.0030 (15)
C7	0.0201 (19)	0.023 (2)	0.0169 (18)	−0.0038 (16)	0.0051 (15)	0.0009 (15)
C8	0.0226 (19)	0.023 (2)	0.0190 (19)	−0.0046 (17)	0.0052 (16)	0.0022 (16)
C9	0.0226 (19)	0.023 (2)	0.0208 (19)	−0.0069 (17)	0.0098 (16)	−0.0026 (16)
C10	0.0216 (19)	0.031 (2)	0.0159 (18)	−0.0067 (17)	0.0038 (15)	0.0004 (16)
C11	0.022 (2)	0.026 (2)	0.0197 (19)	−0.0044 (17)	0.0077 (16)	0.0026 (16)
C12	0.023 (2)	0.022 (2)	0.0208 (19)	−0.0053 (16)	0.0096 (16)	−0.0010 (16)
C13	0.0181 (19)	0.024 (2)	0.0188 (19)	−0.0026 (16)	0.0061 (15)	−0.0002 (15)
C14	0.027 (2)	0.024 (2)	0.0175 (18)	−0.0084 (18)	0.0047 (16)	−0.0023 (15)
C15	0.024 (2)	0.021 (2)	0.0202 (19)	−0.0055 (17)	0.0035 (16)	0.0007 (15)
C16	0.023 (2)	0.0201 (19)	0.029 (2)	−0.0002 (16)	0.0090 (17)	−0.0018 (16)
C17	0.024 (2)	0.0183 (19)	0.029 (2)	−0.0004 (17)	0.0047 (17)	0.0009 (16)
C18	0.024 (2)	0.021 (2)	0.047 (3)	−0.0029 (18)	0.0133 (19)	0.0017 (19)
C19	0.026 (2)	0.018 (2)	0.051 (3)	0.0011 (17)	0.011 (2)	0.0063 (19)
C21	0.061 (4)	0.095 (5)	0.081 (5)	0.012 (4)	0.035 (4)	−0.001 (4)
C20	0.028 (2)	0.033 (2)	0.026 (2)	−0.0043 (19)	0.0015 (18)	0.0067 (18)

Geometric parameters (Å, º)

Fe1—N1^i	2.116 (3)	C5—C6	1.377 (5)
Fe1—N1	2.117 (3)	C5—H5	0.9300
Fe1—N5^ii	2.219 (3)	C6—H6	0.9300
Fe1—N5^iii	2.219 (3)	C7—C8	1.392 (5)
Fe1—N2	2.232 (3)	C7—C12	1.398 (5)
Fe1—N2^i	2.232 (3)	C7—C13	1.499 (5)
S1—C1	1.643 (5)	C8—C9	1.389 (5)
O1—C13	1.220 (5)	C8—H8	0.9300
O2—C14	1.218 (5)	C9—C10	1.384 (6)
O3—C21	1.412 (7)	C9—C14	1.499 (5)
O3—H3	0.8421	C10—C11	1.389 (6)
O4—H4A	0.8493	C10—H10	0.9300
O4—H4B	0.8626	C11—C12	1.392 (5)
N1—C1	1.159 (5)	C11—C20	1.497 (5)
N2—C2	1.334 (5)	C12—H12	0.9300
N2—C6	1.341 (5)	C15—C16	1.385 (5)
N3—C13	1.364 (5)	C15—C19	1.392 (6)
N3—C4	1.404 (5)	C16—C17	1.367 (6)
N3—H3A	0.8600	C16—H16	0.9300
N4—C14	1.363 (5)	C17—H17	0.9300
N4—C15	1.390 (5)	C18—C19	1.365 (6)
N4—H4	0.8600	C18—H18	0.9300
N5—C18	1.336 (5)	C19—H19	0.9300
N5—C17	1.340 (5)	C21—H21A	0.9600
C2—C3	1.369 (6)	C21—H21B	0.9600
C2—H2	0.9300	C21—H21C	0.9600
C3—C4	1.390 (5)	C20—H20A	0.9600
C3—H3B	0.9300	C20—H20B	0.9600
C4—C5	1.389 (5)	C20—H20C	0.9600
N1^i—Fe1—N1	180.0	C9—C8—C7	119.3 (4)
N1^i—Fe1—N5^ii	91.28 (12)	C9—C8—H8	120.3
N1—Fe1—N5^ii	88.72 (12)	C7—C8—H8	120.3
N1^i—Fe1—N5^iii	88.72 (12)	C10—C9—C8	121.0 (4)
N1—Fe1—N5^iii	91.28 (12)	C10—C9—C14	122.4 (4)
N5^ii—Fe1—N5^iii	180.0	C8—C9—C14	116.5 (4)
N1^i—Fe1—N2	90.70 (12)	C9—C10—C11	120.5 (4)
N1—Fe1—N2	89.30 (12)	C9—C10—H10	119.7
N5^ii—Fe1—N2	92.90 (11)	C11—C10—H10	119.7
N5^iii—Fe1—N2	87.10 (11)	C10—C11—C12	118.3 (4)
N1^i—Fe1—N2^i	89.30 (12)	C10—C11—C20	120.8 (4)
N1—Fe1—N2^i	90.70 (12)	C12—C11—C20	120.9 (4)
N5^ii—Fe1—N2^i	87.10 (11)	C11—C12—C7	121.6 (4)
N5^iii—Fe1—N2^i	92.90 (11)	C11—C12—H12	119.2
N2—Fe1—N2^i	180.0	C7—C12—H12	119.2
C21—O3—H3	119.6	O1—C13—N3	122.3 (3)
H4A—O4—H4B	110.0	O1—C13—C7	121.3 (3)
C1—N1—Fe1	174.3 (3)	N3—C13—C7	116.3 (3)
C2—N2—C6	116.1 (3)	O2—C14—N4	124.5 (4)
C2—N2—Fe1	122.0 (3)	O2—C14—C9	122.3 (4)
C6—N2—Fe1	121.9 (2)	N4—C14—C9	113.1 (3)
C13—N3—C4	127.0 (3)	C16—C15—N4	124.6 (4)
C13—N3—H3A	116.5	C16—C15—C19	117.3 (4)
C4—N3—H3A	116.5	N4—C15—C19	118.0 (4)
C14—N4—C15	127.9 (3)	C17—C16—C15	119.0 (4)
C14—N4—H4	116.0	C17—C16—H16	120.5
C15—N4—H4	116.0	C15—C16—H16	120.5
C18—N5—C17	115.9 (3)	N5—C17—C16	124.4 (4)
C18—N5—Fe1^iv	124.4 (3)	N5—C17—H17	117.8
C17—N5—Fe1^iv	119.6 (3)	C16—C17—H17	117.8
N1—C1—S1	179.5 (4)	N5—C18—C19	124.0 (4)
N2—C2—C3	124.1 (4)	N5—C18—H18	118.0
N2—C2—H2	117.9	C19—C18—H18	118.0
C3—C2—H2	117.9	C18—C19—C15	119.5 (4)
C2—C3—C4	119.4 (4)	C18—C19—H19	120.3
C2—C3—H3B	120.3	C15—C19—H19	120.3
C4—C3—H3B	120.3	O3—C21—H21A	109.5
C5—C4—C3	117.4 (3)	O3—C21—H21B	109.5
C5—C4—N3	125.4 (3)	H21A—C21—H21B	109.5
C3—C4—N3	117.2 (3)	O3—C21—H21C	109.5
C6—C5—C4	118.8 (4)	H21A—C21—H21C	109.5
C6—C5—H5	120.6	H21B—C21—H21C	109.5
C4—C5—H5	120.6	C11—C20—H20A	109.5
N2—C6—C5	124.2 (4)	C11—C20—H20B	109.5
N2—C6—H6	117.9	H20A—C20—H20B	109.5
C5—C6—H6	117.9	C11—C20—H20C	109.5
C8—C7—C12	119.1 (3)	H20A—C20—H20C	109.5
C8—C7—C13	123.7 (3)	H20B—C20—H20C	109.5
C12—C7—C13	117.1 (3)
C6—N2—C2—C3	−1.8 (6)	C4—N3—C13—O1	−2.9 (6)
Fe1—N2—C2—C3	175.2 (3)	C4—N3—C13—C7	174.5 (3)
N2—C2—C3—C4	0.5 (7)	C8—C7—C13—O1	177.1 (4)
C2—C3—C4—C5	1.8 (6)	C12—C7—C13—O1	0.9 (5)
C2—C3—C4—N3	−177.0 (4)	C8—C7—C13—N3	−0.3 (5)
C13—N3—C4—C5	21.4 (6)	C12—C7—C13—N3	−176.5 (3)
C13—N3—C4—C3	−160.0 (4)	C15—N4—C14—O2	−6.8 (6)
C3—C4—C5—C6	−2.6 (6)	C15—N4—C14—C9	169.1 (4)
N3—C4—C5—C6	176.0 (4)	C10—C9—C14—O2	−128.8 (4)
C2—N2—C6—C5	0.9 (6)	C8—C9—C14—O2	55.0 (5)
Fe1—N2—C6—C5	−176.1 (3)	C10—C9—C14—N4	55.2 (5)
C4—C5—C6—N2	1.3 (6)	C8—C9—C14—N4	−121.0 (4)
C12—C7—C8—C9	5.2 (6)	C14—N4—C15—C16	1.1 (6)
C13—C7—C8—C9	−171.0 (3)	C14—N4—C15—C19	−174.9 (4)
C7—C8—C9—C10	−3.4 (6)	N4—C15—C16—C17	−177.2 (4)
C7—C8—C9—C14	172.9 (3)	C19—C15—C16—C17	−1.1 (6)
C8—C9—C10—C11	−1.0 (6)	C18—N5—C17—C16	1.2 (6)
C14—C9—C10—C11	−177.0 (4)	Fe1^iv—N5—C17—C16	179.7 (3)
C9—C10—C11—C12	3.4 (6)	C15—C16—C17—N5	0.3 (6)
C9—C10—C11—C20	−175.9 (4)	C17—N5—C18—C19	−1.9 (6)
C10—C11—C12—C7	−1.6 (6)	Fe1^iv—N5—C18—C19	179.7 (3)
C20—C11—C12—C7	177.7 (4)	N5—C18—C19—C15	1.1 (7)
C8—C7—C12—C11	−2.7 (6)	C16—C15—C19—C18	0.5 (6)
C13—C7—C12—C11	173.7 (3)	N4—C15—C19—C18	176.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
N3—H3A···O4	0.86	2.17	2.995 (5)	162
N4—H4···O1^vii	0.86	2.11	2.942 (4)	164
C3—H3B···O4	0.93	2.54	3.263 (5)	135
C5—H5···O1	0.93	2.34	2.876 (5)	117
C6—H6···O3^viii	0.93	2.56	3.340 (6)	142
C16—H16···O2	0.93	2.28	2.870 (5)	121
C17—H17···N1^iv	0.93	2.60	3.162 (5)	119
C18—H18···N1^ix	0.93	2.65	3.166 (5)	116
C19—H19···O1^vii	0.93	2.51	3.274 (5)	140
C21—H21B···S1	0.96	2.96	3.502 (7)	117
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
N3—H3A···O4	0.86	2.17	2.995 (5)	162
N4—H4···O1^vii	0.86	2.11	2.942 (4)	164
C3—H3B···O4	0.93	2.54	3.263 (5)	135
C5—H5···O1	0.93	2.34	2.876 (5)	117
C6—H6···O3^viii	0.93	2.56	3.340 (6)	142
C16—H16···O2	0.93	2.28	2.870 (5)	121
C17—H17···N1^iv	0.93	2.60	3.162 (5)	119
C18—H18···N1^ix	0.93	2.65	3.166 (5)	116
C19—H19···O1^vii	0.93	2.51	3.274 (5)	140
C21—H21B···S1	0.96	2.96	3.502 (7)	117
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
N3—H3A···O4	0.86	2.17	2.995 (5)	162
N4—H4···O1^vii	0.86	2.11	2.942 (4)	164
C3—H3B···O4	0.93	2.54	3.263 (5)	135
C5—H5···O1	0.93	2.34	2.876 (5)	117
C6—H6···O3^viii	0.93	2.56	3.340 (6)	142
C16—H16···O2	0.93	2.28	2.870 (5)	121
C17—H17···N1^iv	0.93	2.60	3.162 (5)	119
C18—H18···N1^ix	0.93	2.65	3.166 (5)	116
C19—H19···O1^vii	0.93	2.51	3.274 (5)	140
C21—H21B···S1	0.96	2.96	3.502 (7)	117
O4—H4A···O3^vi	0.85	2.09	2.712 (6)	129
O4—H4B···S1^v	0.86	2.48	3.324 (4)	165
N3—H3A···O4	0.86	2.17	2.995 (5)	162
N4—H4···O1^vii	0.86	2.11	2.942 (4)	164
C3—H3B···O4	0.93	2.54	3.263 (5)	135
C5—H5···O1	0.93	2.34	2.876 (5)	117
C6—H6···O3^viii	0.93	2.56	3.340 (6)	142
C16—H16···O2	0.93	2.28	2.870 (5)	121
C17—H17···N1^iv	0.93	2.60	3.162 (5)	119
C18—H18···N1^ix	0.93	2.65	3.166 (5)	116
C19—H19···O1^vii	0.93	2.51	3.274 (5)	140
C21—H21B···S1	0.96	2.96	3.502 (7)	117
O3—H3···O2^x	0.84	1.98	2.805 (5)	166

Symmetry codes: (iv) −x+1/2, y+1/2, −z+3/2; (v) x+1/2, −y+1/2, z+1/2; (vi) x−1/2, −y+1/2, z+1/2; (vii) −x+1, −y, −z+2; (viii) −x, −y, −z+1; (ix) x+3/2, −y+1/2, z+1/2; (x) x, y, z−1.