Bis(ethanol-κO)bis-(pyridine-3-carb-aldehyde-κN thio-semicarbazone)bis-(thio-cyanato-κN)iron(II)-pyridine-3-carbaldehyde thio-semicarbazone (1/2).

The crystal structure of the title Fe(II) complex, [Fe(NCS)(2)(C(7)H(8)N(4)S)(2)(CH(3)CH(2)OH)(2)]·2C(7)H(8)N(4)S, based on the Schiff base ligand pyridine-3-carbaldehyde thio-semicarbazone (pct), results from the cocrystallization of an Fe(II) coordination compound together with two of the pct ligands. The complex unit is mononuclear, with the central Fe(II) ion located on a crystallographic centre of inversion and coordinated by four N atoms from two pct ligands and two thio-cyanate anions. The slightly distorted octa-hedral coordination is completed by two O atoms from ethanol mol-ecules. The crystal packing is accomplished inter-molecular N-H⋯S hydrogen bonds.

Related literature

For the structures of metal complexes of Schiff base ligands synthesized by condensation of pyridine-3-carbaldehyde and amino compounds, see: Brook et al. (2000 ▶); Deng et al. (2007 ▶); Garbelini et al. (2008 ▶); Kowol et al. (2007 ▶); Zhong et al. (2007 ▶). For the corresponding Mn(II) complex of pyridine-3-carbaldehyde thio­semicarbazone, see: Li et al. (2006 ▶).

Experimental

Crystal data

[Fe(NCS)2(C7H8N4S)2(C2H6O)2]·2C7H8N4S

M = 985.08

Triclinic,

a = 8.916 (4) Å

b = 9.556 (5) Å

c = 14.538 (7) Å

α = 87.341 (8)°

β = 88.191 (8)°

γ = 69.604 (8)°

V = 1160 (1) Å3

Z = 1

Mo Kα radiation

μ = 0.65 mm−1

T = 173 K

0.32 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.819, T max = 0.871

8300 measured reflections

4037 independent reflections

2953 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.134

S = 1.01

4037 reflections

282 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024076/im2122sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024076/im2122Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe(NCS)2(C7H8N4S)2(C2H6O)2]·2C7H8N4S	Z = 1
Mr = 985.08	F(000) = 512
Triclinic, P1	Dx = 1.411 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.916 (4) Å	Cell parameters from 3773 reflections
b = 9.556 (5) Å	θ = 2.3–26.9°
c = 14.538 (7) Å	µ = 0.65 mm−1
α = 87.341 (8)°	T = 173 K
β = 88.191 (8)°	Block, dark green
γ = 69.604 (8)°	0.32 × 0.26 × 0.22 mm
V = 1160 (1) Å3

Bruker SMART CCD area-detector diffractometer	4037 independent reflections
Radiation source: fine-focus sealed tube	2953 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.819, Tmax = 0.871	k = −11→11
8300 measured reflections	l = −17→17

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.082P)2 + 0.3403P] where P = (Fo2 + 2Fc2)/3
4037 reflections	(Δ/σ)max = 0.001
282 parameters	Δρmax = 0.43 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
Fe1	0.5000	0.0000	0.0000	0.0416 (2)
N1	0.2848 (3)	0.1196 (3)	0.09806 (16)	0.0410 (6)
N2	0.1975 (3)	−0.0995 (3)	0.33648 (15)	0.0389 (6)
N3	0.1640 (3)	−0.1698 (3)	0.41443 (16)	0.0413 (6)
H3	0.0676	−0.1382	0.4397	0.050*
N4	0.4186 (3)	−0.3344 (3)	0.40767 (19)	0.0659 (9)
H4A	0.4316	−0.2885	0.3557	0.079*
H4B	0.4981	−0.4112	0.4298	0.079*
N5	0.5606 (3)	−0.2022 (3)	0.08302 (19)	0.0536 (7)
C12	0.7900 (4)	0.3134 (4)	0.8792 (2)	0.0604 (9)
H12	0.6944	0.3331	0.9150	0.072*
N7	0.8316 (3)	0.5754 (3)	0.64455 (16)	0.0424 (6)
N8	0.8582 (3)	0.6617 (3)	0.57213 (17)	0.0453 (6)
H8	0.9546	0.6403	0.5474	0.054*
N9	0.5924 (3)	0.7961 (3)	0.5738 (2)	0.0652 (8)
H9A	0.5814	0.7316	0.6163	0.078*
H9B	0.5080	0.8711	0.5547	0.078*
O1	0.6741 (3)	0.0634 (3)	0.07601 (15)	0.0541 (6)
S1	0.24701 (9)	−0.36692 (9)	0.55347 (5)	0.0500 (2)
S2	0.64184 (10)	−0.43494 (10)	0.21504 (7)	0.0632 (3)
S3	0.76674 (9)	0.89666 (9)	0.45668 (6)	0.0525 (3)
C1	0.1770 (4)	0.2554 (3)	0.0754 (2)	0.0457 (7)
H1	0.1962	0.3076	0.0218	0.055*
C2	0.0403 (4)	0.3210 (3)	0.1271 (2)	0.0471 (7)
H2	−0.0332	0.4165	0.1092	0.057*
C3	0.0117 (3)	0.2462 (3)	0.20499 (19)	0.0416 (7)
H3A	−0.0815	0.2902	0.2418	0.050*
C4	0.1196 (3)	0.1064 (3)	0.22943 (18)	0.0354 (6)
C5	0.2540 (3)	0.0486 (3)	0.17329 (19)	0.0405 (7)
H5	0.3286	−0.0473	0.1895	0.049*
C6	0.0921 (3)	0.0255 (3)	0.3116 (2)	0.0409 (7)
H6	−0.0039	0.0653	0.3468	0.049*
C7	0.2808 (3)	−0.2882 (3)	0.4521 (2)	0.0424 (7)
C8	0.5957 (3)	−0.2995 (3)	0.1376 (2)	0.0409 (7)
C9	0.6438 (4)	0.1960 (4)	0.1234 (2)	0.0602 (9)
H9C	0.5507	0.2751	0.0956	0.072*
H9D	0.7375	0.2286	0.1155	0.072*
C10	0.6107 (5)	0.1792 (5)	0.2242 (3)	0.0809 (13)
H10A	0.5138	0.1535	0.2327	0.121*
H10B	0.5952	0.2735	0.2538	0.121*
H10C	0.7015	0.0997	0.2521	0.121*
C11	0.9244 (4)	0.1953 (4)	0.9025 (2)	0.0577 (9)
H11	0.9201	0.1350	0.9557	0.069*
N6	1.0609 (3)	0.1611 (3)	0.85410 (18)	0.0512 (7)
C13	1.0645 (4)	0.2479 (3)	0.7803 (2)	0.0457 (7)
H13	1.1613	0.2244	0.7453	0.055*
C14	0.9344 (3)	0.3714 (3)	0.7514 (2)	0.0404 (7)
C15	0.7945 (4)	0.4035 (4)	0.8032 (2)	0.0533 (8)
H15	0.7026	0.4867	0.7865	0.064*
C16	0.9506 (3)	0.4637 (3)	0.6721 (2)	0.0419 (7)
H16	1.0508	0.4406	0.6406	0.050*
C17	0.7345 (3)	0.7807 (3)	0.53873 (19)	0.0417 (7)
H17	0.747 (3)	−0.006 (3)	0.099 (2)	0.067 (12)*

	U11	U22	U33	U12	U13	U23
Fe1	0.0384 (3)	0.0424 (4)	0.0381 (4)	−0.0086 (3)	0.0034 (2)	0.0106 (3)
N1	0.0387 (13)	0.0410 (14)	0.0383 (13)	−0.0092 (11)	0.0062 (10)	0.0063 (11)
N2	0.0372 (13)	0.0431 (14)	0.0345 (13)	−0.0130 (11)	0.0060 (10)	0.0047 (11)
N3	0.0344 (13)	0.0445 (14)	0.0391 (13)	−0.0085 (11)	0.0080 (10)	0.0102 (11)
N4	0.0418 (15)	0.073 (2)	0.0584 (18)	0.0057 (14)	0.0150 (13)	0.0275 (15)
N5	0.0464 (16)	0.0499 (16)	0.0545 (16)	−0.0076 (12)	0.0044 (12)	0.0220 (14)
C12	0.0473 (19)	0.075 (2)	0.058 (2)	−0.0233 (18)	0.0052 (16)	0.0173 (18)
N7	0.0404 (14)	0.0469 (15)	0.0407 (14)	−0.0173 (12)	−0.0005 (11)	0.0076 (11)
N8	0.0379 (13)	0.0464 (15)	0.0485 (15)	−0.0129 (11)	0.0044 (11)	0.0104 (12)
N9	0.0362 (15)	0.071 (2)	0.0734 (19)	−0.0046 (13)	0.0092 (13)	0.0306 (16)
O1	0.0492 (14)	0.0503 (14)	0.0551 (14)	−0.0065 (11)	−0.0113 (11)	−0.0028 (11)
S1	0.0399 (4)	0.0577 (5)	0.0429 (5)	−0.0078 (4)	0.0058 (3)	0.0164 (4)
S2	0.0511 (5)	0.0507 (5)	0.0736 (6)	−0.0045 (4)	0.0042 (4)	0.0327 (4)
S3	0.0410 (4)	0.0548 (5)	0.0520 (5)	−0.0077 (4)	0.0059 (4)	0.0184 (4)
C1	0.0456 (17)	0.0447 (17)	0.0418 (17)	−0.0112 (14)	0.0055 (13)	0.0094 (14)
C2	0.0442 (17)	0.0364 (16)	0.0482 (18)	0.0007 (13)	0.0010 (14)	0.0061 (14)
C3	0.0349 (15)	0.0430 (17)	0.0404 (16)	−0.0061 (13)	0.0061 (12)	−0.0018 (13)
C4	0.0319 (14)	0.0388 (15)	0.0347 (15)	−0.0115 (12)	0.0024 (11)	−0.0008 (12)
C5	0.0370 (15)	0.0333 (15)	0.0431 (16)	−0.0036 (12)	0.0037 (12)	0.0090 (13)
C6	0.0350 (15)	0.0429 (17)	0.0403 (16)	−0.0090 (13)	0.0086 (12)	0.0013 (13)
C7	0.0378 (16)	0.0458 (17)	0.0401 (16)	−0.0114 (13)	0.0033 (13)	0.0044 (13)
C8	0.0312 (14)	0.0402 (17)	0.0454 (17)	−0.0063 (12)	0.0083 (12)	0.0018 (14)
C9	0.066 (2)	0.062 (2)	0.059 (2)	−0.0292 (19)	−0.0024 (17)	−0.0029 (18)
C10	0.103 (3)	0.092 (3)	0.063 (3)	−0.054 (3)	0.015 (2)	−0.007 (2)
C11	0.060 (2)	0.064 (2)	0.053 (2)	−0.0279 (18)	−0.0082 (17)	0.0184 (17)
N6	0.0501 (16)	0.0493 (16)	0.0521 (16)	−0.0155 (13)	−0.0111 (13)	0.0132 (13)
C13	0.0415 (17)	0.0480 (18)	0.0475 (18)	−0.0159 (14)	−0.0004 (13)	0.0023 (14)
C14	0.0389 (16)	0.0409 (17)	0.0428 (16)	−0.0161 (13)	−0.0033 (13)	0.0042 (13)
C15	0.0388 (17)	0.056 (2)	0.060 (2)	−0.0117 (15)	−0.0008 (15)	0.0154 (16)
C16	0.0389 (16)	0.0433 (17)	0.0438 (17)	−0.0157 (14)	0.0018 (13)	0.0029 (13)
C17	0.0406 (16)	0.0466 (17)	0.0365 (16)	−0.0139 (13)	0.0010 (13)	0.0025 (13)

Fe1—N5i	2.140 (3)	S1—C7	1.690 (3)
Fe1—N5	2.140 (3)	S2—C8	1.623 (3)
Fe1—O1i	2.196 (2)	S3—C17	1.677 (3)
Fe1—O1	2.196 (2)	C1—C2	1.377 (4)
Fe1—N1	2.339 (2)	C1—H1	0.9500
Fe1—N1i	2.339 (2)	C2—C3	1.375 (4)
N1—C5	1.332 (3)	C2—H2	0.9500
N1—C1	1.352 (4)	C3—C4	1.385 (4)
N2—C6	1.280 (4)	C3—H3A	0.9500
N2—N3	1.368 (3)	C4—C5	1.388 (4)
N3—C7	1.350 (4)	C4—C6	1.453 (4)
N3—H3	0.8800	C5—H5	0.9500
N4—C7	1.312 (4)	C6—H6	0.9500
N4—H4A	0.8800	C9—C10	1.498 (5)
N4—H4B	0.8800	C9—H9C	0.9900
N5—C8	1.156 (4)	C9—H9D	0.9900
C12—C11	1.368 (5)	C10—H10A	0.9800
C12—C15	1.377 (4)	C10—H10B	0.9800
C12—H12	0.9500	C10—H10C	0.9800
N7—C16	1.274 (4)	C11—N6	1.332 (4)
N7—N8	1.373 (3)	C11—H11	0.9500
N8—C17	1.361 (4)	N6—C13	1.332 (4)
N8—H8	0.8800	C13—C14	1.395 (4)
N9—C17	1.312 (4)	C13—H13	0.9500
N9—H9A	0.8800	C14—C15	1.383 (4)
N9—H9B	0.8800	C14—C16	1.453 (4)
O1—C9	1.408 (4)	C15—H15	0.9500
O1—H17	0.816 (10)	C16—H16	0.9500
N5i—Fe1—N5	180.00 (14)	C2—C3—H3A	120.2
N5i—Fe1—O1i	88.99 (10)	C4—C3—H3A	120.2
N5—Fe1—O1i	91.01 (10)	C3—C4—C5	117.5 (2)
N5i—Fe1—O1	91.01 (10)	C3—C4—C6	120.6 (2)
N5—Fe1—O1	88.99 (10)	C5—C4—C6	121.9 (3)
O1i—Fe1—O1	180.00 (14)	N1—C5—C4	123.9 (3)
N5i—Fe1—N1	88.53 (9)	N1—C5—H5	118.0
N5—Fe1—N1	91.47 (9)	C4—C5—H5	118.0
O1i—Fe1—N1	85.58 (9)	N2—C6—C4	119.9 (2)
O1—Fe1—N1	94.42 (9)	N2—C6—H6	120.0
N5i—Fe1—N1i	91.47 (9)	C4—C6—H6	120.0
N5—Fe1—N1i	88.53 (9)	N4—C7—N3	116.9 (3)
O1i—Fe1—N1i	94.42 (9)	N4—C7—S1	123.1 (2)
O1—Fe1—N1i	85.58 (9)	N3—C7—S1	119.9 (2)
N1—Fe1—N1i	180.00 (12)	N5—C8—S2	179.0 (3)
C5—N1—C1	117.4 (2)	O1—C9—C10	113.3 (3)
C5—N1—Fe1	120.69 (18)	O1—C9—H9C	108.9
C1—N1—Fe1	121.52 (18)	C10—C9—H9C	108.9
C6—N2—N3	116.9 (2)	O1—C9—H9D	108.9
C7—N3—N2	119.2 (2)	C10—C9—H9D	108.9
C7—N3—H3	120.4	H9C—C9—H9D	107.7
N2—N3—H3	120.4	C9—C10—H10A	109.5
C7—N4—H4A	120.0	C9—C10—H10B	109.5
C7—N4—H4B	120.0	H10A—C10—H10B	109.5
H4A—N4—H4B	120.0	C9—C10—H10C	109.5
C8—N5—Fe1	170.5 (3)	H10A—C10—H10C	109.5
C11—C12—C15	119.4 (3)	H10B—C10—H10C	109.5
C11—C12—H12	120.3	N6—C11—C12	122.9 (3)
C15—C12—H12	120.3	N6—C11—H11	118.5
C16—N7—N8	117.2 (2)	C12—C11—H11	118.5
C17—N8—N7	119.6 (2)	C11—N6—C13	117.4 (3)
C17—N8—H8	120.2	N6—C13—C14	123.9 (3)
N7—N8—H8	120.2	N6—C13—H13	118.1
C17—N9—H9A	120.0	C14—C13—H13	118.1
C17—N9—H9B	120.0	C15—C14—C13	117.1 (3)
H9A—N9—H9B	120.0	C15—C14—C16	122.6 (3)
C9—O1—Fe1	126.7 (2)	C13—C14—C16	120.3 (3)
C9—O1—H17	112 (3)	C12—C15—C14	119.2 (3)
Fe1—O1—H17	115 (3)	C12—C15—H15	120.4
N1—C1—C2	122.6 (3)	C14—C15—H15	120.4
N1—C1—H1	118.7	N7—C16—C14	120.5 (3)
C2—C1—H1	118.7	N7—C16—H16	119.7
C3—C2—C1	119.1 (3)	C14—C16—H16	119.7
C3—C2—H2	120.5	N9—C17—N8	116.1 (3)
C1—C2—H2	120.5	N9—C17—S3	123.4 (2)
C2—C3—C4	119.6 (3)	N8—C17—S3	120.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9B···S3ii	0.88	2.67	3.533 (3)	165
N4—H4B···S1iii	0.88	2.52	3.373 (3)	164
N4—H4A···S2	0.88	2.80	3.360 (3)	123
N3—H3···S3iv	0.88	2.59	3.414 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9B⋯S3i	0.88	2.67	3.533 (3)	165
N4—H4B⋯S1ii	0.88	2.52	3.373 (3)	164
N4—H4A⋯S2	0.88	2.80	3.360 (3)	123
N3—H3⋯S3iii	0.88	2.59	3.414 (3)	156

Symmetry codes: (i) ; (ii) ; (iii) .