Synthesis, crystal structure and properties of tetra­kis­(pyridine-3-carbo­nitrile)­dithio­cyanatoiron(II) and of diaqua­bis­(pyridine-3-carbo­nitrile)­di­thio­cyanatoiron(II) pyridine-3-carbo­nitrile monosolvate

Two complexes, 1 and 2, based on Fe(NCS)₂ and 3-cyano­pyridine as coligand were synthesized, structurally characterized and investigated for their thermal behavior. In both compounds the Fe^II cations are octa­hedrally coordinated by two N-bonded thio­cyanate anions in trans-position as well as four 3-cyano­pyridine coligands for compound 1 and two 3-cyano­pyridine ligands and two water mol­ecules for compound 2. Upon heating, both complexes transform into an inter­mediate with bridging anionic ligands that is isotypic to its Cd(NCS)₂ and Mn(NCS)₂ analogs.

Key indicators

Structure: 1

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.074
• Data-to-parameter ratio = 16.3

Structure: 2

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.022
• wR factor = 0.060
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Datablock: 1


Alert level C
PLAT767_ALERT_4_C INS Embedded LIST 6 Instruction Should be LIST 4     Please Check

Alert level G
PLAT142_ALERT_4_G s.u. on b - Axis Small or Missing ..............    0.00010 Ang.
PLAT143_ALERT_4_G s.u. on c - Axis Small or Missing ..............    0.00010 Ang.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C1       .        7.2 s.u.
PLAT432_ALERT_2_G Short Inter X...Y Contact  S1       ..C21      .       3.28 Ang.
                                             1-x,1-y,-1/2+z  =      2_664 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H11      ..N1       .       2.63 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H24      ..N22      .       2.67 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H31      ..N1       .       2.67 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H35      ..N12      .       2.67 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Fe1       (II)      .       1.96 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         31 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: 2


Alert level C
PLAT767_ALERT_4_C INS Embedded LIST 6 Instruction Should be LIST 4     Please Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         13 Report

Alert level G
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.001 Degree
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C1       .       12.5 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    N1       --C1       .        8.1 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C12      --C16      .        6.1 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe1      --O1       .        8.2 s.u.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H11      ..S1       .       3.03 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H14      ..S1       .       2.98 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H15      ..N1       .       2.67 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H21      ..S1       .       2.92 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H24      ..N22      .       2.67 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H25      ..S1       .       3.01 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Fe1       (II)      .       2.03 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         86 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrysAlis PRO 1.171.42.90a (Rigaku OD, 2023) for (1); CrysAlis PRO 1.171.42.100a (Rigaku OD, 2023) for (2). Cell refinement: CrysAlis PRO 1.171.42.90a (Rigaku OD, 2023) for (1); CrysAlis PRO 1.171.42.100a (Rigaku OD, 2023) for (2). Data reduction: CrysAlis PRO 1.171.42.90a (Rigaku OD, 2023) for (1); CrysAlis PRO 1.171.42.100a (Rigaku OD, 2023) for (2). For both structures, program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015a); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Tetrakis(pyridine-3-carbonitrile)dithiocyanatoiron(II) (1)

Crystal data

[Fe(NCS)2(C6H4N2)4]	Dx = 1.444 Mg m^−3
Mr = 588.46	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pna21	Cell parameters from 22008 reflections
a = 20.3549 (2) Å	θ = 4.3–79.7°
b = 10.2084 (1) Å	µ = 6.21 mm^−1
c = 13.0310 (1) Å	T = 100 K
V = 2707.72 (4) Å^3	Block, yellow
Z = 4	0.10 × 0.08 × 0.06 mm
F(000) = 1200

Data collection

XtaLAB Synergy, Dualflex, HyPix diffractometer	5727 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	5676 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 10.0000 pixels mm^-1	θmax = 80.1°, θmin = 4.3°
ω scans	h = −25→24
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2023)	k = −13→13
Tmin = 0.745, Tmax = 1.000	l = −16→15
26794 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0521P)^2 + 0.7383P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.24 e Å^−3
5727 reflections	Δρmin = −0.29 e Å^−3
352 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
1 restraint	Absolute structure parameter: −0.001 (3)
Primary atom site location: dual

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.

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

	x	y	z	Uiso*/Ueq
Fe1	0.61644 (2)	0.57715 (4)	0.50208 (3)	0.01625 (10)
N1	0.60947 (11)	0.5803 (2)	0.34404 (18)	0.0220 (5)
C1	0.60437 (12)	0.5722 (2)	0.2549 (2)	0.0182 (5)
S1	0.59757 (3)	0.56051 (6)	0.13118 (5)	0.02232 (13)
N2	0.62205 (11)	0.5735 (2)	0.66062 (18)	0.0207 (5)
C2	0.61060 (12)	0.5872 (2)	0.7474 (2)	0.0184 (5)
S2	0.59268 (4)	0.60626 (6)	0.86779 (5)	0.02877 (15)
N11	0.51976 (9)	0.68579 (19)	0.51593 (16)	0.0186 (4)
C11	0.47464 (12)	0.6794 (2)	0.44172 (17)	0.0193 (4)
H11	0.485160	0.634024	0.380244	0.023*
C12	0.41249 (12)	0.7369 (2)	0.45077 (19)	0.0203 (5)
C13	0.39634 (12)	0.8027 (2)	0.5405 (2)	0.0218 (5)
H13	0.354112	0.840674	0.549291	0.026*
C14	0.44349 (12)	0.8114 (2)	0.61682 (19)	0.0227 (5)
H14	0.434368	0.856933	0.678783	0.027*
C15	0.50423 (12)	0.7527 (2)	0.60161 (18)	0.0214 (5)
H15	0.536372	0.760156	0.654147	0.026*
C16	0.36587 (13)	0.7271 (2)	0.3681 (2)	0.0233 (5)
N12	0.32775 (12)	0.7231 (2)	0.30298 (19)	0.0312 (5)
N21	0.57491 (9)	0.37054 (19)	0.50576 (17)	0.0190 (4)
C21	0.54990 (11)	0.3198 (2)	0.59197 (19)	0.0198 (4)
H21	0.547628	0.373602	0.651370	0.024*
C22	0.52700 (11)	0.1912 (2)	0.59825 (19)	0.0210 (5)
C23	0.53071 (12)	0.1103 (2)	0.5122 (2)	0.0244 (5)
H23	0.516095	0.021992	0.514719	0.029*
C24	0.55633 (13)	0.1629 (2)	0.4232 (2)	0.0258 (5)
H24	0.559409	0.111195	0.362787	0.031*
C25	0.57755 (13)	0.2922 (2)	0.4227 (2)	0.0231 (5)
H25	0.594798	0.327145	0.360763	0.028*
C26	0.49712 (13)	0.1461 (3)	0.6918 (2)	0.0250 (5)
N22	0.47136 (13)	0.1104 (2)	0.7652 (2)	0.0325 (5)
N31	0.71545 (9)	0.4783 (2)	0.49342 (16)	0.0208 (4)
C31	0.75413 (12)	0.4869 (2)	0.4104 (2)	0.0219 (5)
H31	0.738616	0.533481	0.352142	0.026*
C32	0.81617 (13)	0.4300 (2)	0.4066 (2)	0.0237 (5)
C33	0.84021 (12)	0.3634 (3)	0.4921 (2)	0.0275 (5)
H33	0.882745	0.325046	0.491573	0.033*
C34	0.80029 (14)	0.3547 (3)	0.5778 (2)	0.0293 (5)
H34	0.815036	0.310288	0.637584	0.035*
C35	0.73825 (13)	0.4119 (2)	0.5752 (2)	0.0248 (5)
H35	0.710769	0.403611	0.633745	0.030*
C36	0.85443 (14)	0.4395 (3)	0.3136 (2)	0.0285 (6)
N32	0.88400 (12)	0.4469 (3)	0.2389 (2)	0.0368 (6)
N41	0.67037 (9)	0.76769 (19)	0.49903 (17)	0.0190 (4)
C41	0.66633 (11)	0.8538 (2)	0.42188 (19)	0.0212 (4)
H41	0.635285	0.838771	0.368733	0.025*
C42	0.70611 (12)	0.9649 (3)	0.4167 (2)	0.0220 (5)
C43	0.75141 (12)	0.9892 (3)	0.4943 (2)	0.0263 (5)
H43	0.779162	1.064013	0.492090	0.032*
C44	0.75473 (13)	0.9008 (3)	0.5748 (2)	0.0273 (5)
H44	0.784604	0.914585	0.629764	0.033*
C45	0.71398 (12)	0.7922 (3)	0.5742 (2)	0.0229 (5)
H45	0.716965	0.731957	0.629611	0.027*
C46	0.70086 (13)	1.0523 (3)	0.3298 (2)	0.0260 (5)
N42	0.69645 (12)	1.1210 (3)	0.2610 (2)	0.0350 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01820 (17)	0.01806 (17)	0.01250 (17)	−0.00105 (13)	0.00061 (15)	0.00084 (13)
N1	0.0273 (11)	0.0241 (11)	0.0147 (12)	0.0001 (8)	−0.0005 (8)	0.0004 (7)
C1	0.0154 (10)	0.0165 (11)	0.0225 (15)	0.0006 (8)	0.0018 (9)	0.0016 (9)
S1	0.0246 (3)	0.0278 (3)	0.0145 (3)	0.0040 (2)	−0.0001 (2)	−0.0018 (2)
N2	0.0233 (10)	0.0220 (11)	0.0167 (11)	−0.0001 (8)	−0.0013 (7)	0.0010 (7)
C2	0.0208 (11)	0.0159 (11)	0.0185 (14)	−0.0020 (8)	−0.0029 (9)	0.0024 (9)
S2	0.0467 (4)	0.0235 (3)	0.0162 (3)	−0.0019 (3)	0.0055 (3)	−0.0007 (3)
N11	0.0195 (8)	0.0169 (9)	0.0196 (10)	−0.0021 (7)	0.0008 (7)	0.0002 (7)
C11	0.0222 (11)	0.0183 (10)	0.0175 (11)	−0.0019 (8)	0.0008 (8)	0.0011 (8)
C12	0.0210 (11)	0.0187 (11)	0.0210 (12)	−0.0023 (8)	−0.0002 (9)	0.0008 (9)
C13	0.0233 (11)	0.0177 (11)	0.0243 (12)	−0.0001 (9)	0.0002 (9)	0.0006 (9)
C14	0.0286 (12)	0.0189 (11)	0.0206 (12)	0.0012 (9)	−0.0004 (9)	−0.0040 (9)
C15	0.0251 (11)	0.0193 (10)	0.0199 (11)	−0.0022 (9)	−0.0021 (9)	−0.0013 (9)
C16	0.0260 (12)	0.0195 (11)	0.0245 (12)	0.0018 (9)	−0.0002 (10)	0.0001 (10)
N12	0.0324 (12)	0.0298 (11)	0.0314 (13)	0.0020 (10)	−0.0101 (10)	−0.0030 (9)
N21	0.0187 (8)	0.0200 (9)	0.0182 (9)	−0.0009 (7)	0.0006 (7)	0.0000 (8)
C21	0.0197 (10)	0.0197 (11)	0.0201 (11)	−0.0005 (8)	0.0015 (8)	−0.0020 (9)
C22	0.0197 (10)	0.0203 (11)	0.0230 (12)	0.0006 (8)	0.0039 (9)	0.0018 (9)
C23	0.0264 (11)	0.0193 (11)	0.0276 (13)	−0.0010 (9)	0.0038 (10)	−0.0011 (10)
C24	0.0327 (13)	0.0204 (12)	0.0244 (12)	−0.0013 (10)	0.0036 (10)	−0.0037 (10)
C25	0.0284 (12)	0.0219 (12)	0.0191 (11)	0.0001 (9)	0.0037 (9)	0.0001 (9)
C26	0.0284 (12)	0.0185 (11)	0.0280 (13)	−0.0004 (9)	0.0060 (10)	−0.0019 (10)
N22	0.0417 (14)	0.0225 (11)	0.0333 (13)	−0.0015 (9)	0.0141 (10)	0.0011 (9)
N31	0.0208 (9)	0.0207 (9)	0.0210 (10)	0.0006 (7)	0.0005 (8)	0.0005 (8)
C31	0.0219 (11)	0.0206 (11)	0.0232 (11)	−0.0020 (9)	0.0021 (9)	−0.0010 (9)
C32	0.0223 (12)	0.0216 (12)	0.0274 (14)	−0.0017 (9)	0.0038 (10)	−0.0050 (9)
C33	0.0246 (11)	0.0255 (11)	0.0324 (14)	0.0068 (10)	−0.0025 (10)	−0.0063 (10)
C34	0.0328 (13)	0.0287 (13)	0.0263 (13)	0.0102 (11)	−0.0037 (10)	−0.0002 (11)
C35	0.0278 (12)	0.0248 (11)	0.0219 (12)	0.0048 (10)	0.0026 (10)	−0.0001 (10)
C36	0.0234 (13)	0.0257 (12)	0.0363 (15)	0.0005 (9)	0.0058 (11)	−0.0049 (11)
N32	0.0333 (13)	0.0315 (12)	0.0456 (16)	0.0010 (9)	0.0146 (11)	−0.0031 (11)
N41	0.0182 (8)	0.0193 (9)	0.0196 (8)	−0.0012 (7)	−0.0011 (8)	0.0018 (8)
C41	0.0195 (10)	0.0224 (11)	0.0217 (11)	0.0011 (9)	−0.0003 (9)	0.0011 (10)
C42	0.0212 (10)	0.0228 (11)	0.0221 (12)	0.0003 (9)	0.0037 (9)	0.0042 (10)
C43	0.0231 (11)	0.0271 (12)	0.0288 (13)	−0.0069 (9)	0.0007 (10)	0.0023 (10)
C44	0.0240 (12)	0.0329 (13)	0.0250 (13)	−0.0080 (10)	−0.0047 (10)	0.0025 (11)
C45	0.0230 (11)	0.0242 (11)	0.0215 (11)	−0.0018 (9)	−0.0030 (9)	0.0028 (10)
C46	0.0241 (12)	0.0241 (12)	0.0297 (14)	−0.0011 (9)	0.0041 (10)	0.0039 (11)
N42	0.0339 (12)	0.0356 (13)	0.0356 (14)	−0.0006 (10)	0.0048 (10)	0.0130 (11)

Geometric parameters (Å, º)

Fe1—N1	2.065 (2)	C23—C24	1.380 (4)
Fe1—N2	2.069 (2)	C24—H24	0.9500
Fe1—N11	2.2660 (19)	C24—C25	1.389 (4)
Fe1—N21	2.273 (2)	C25—H25	0.9500
Fe1—N31	2.257 (2)	C26—N22	1.149 (4)
Fe1—N41	2.2339 (19)	N31—C31	1.341 (3)
N1—C1	1.169 (4)	N31—C35	1.346 (3)
C1—S1	1.622 (3)	C31—H31	0.9500
N2—C2	1.163 (4)	C31—C32	1.391 (4)
C2—S2	1.622 (3)	C32—C33	1.394 (4)
N11—C11	1.335 (3)	C32—C36	1.444 (4)
N11—C15	1.347 (3)	C33—H33	0.9500
C11—H11	0.9500	C33—C34	1.384 (4)
C11—C12	1.399 (3)	C34—H34	0.9500
C12—C13	1.388 (3)	C34—C35	1.392 (4)
C12—C16	1.439 (3)	C35—H35	0.9500
C13—H13	0.9500	C36—N32	1.146 (4)
C13—C14	1.385 (4)	N41—C41	1.338 (3)
C14—H14	0.9500	N41—C45	1.345 (3)
C14—C15	1.388 (3)	C41—H41	0.9500
C15—H15	0.9500	C41—C42	1.395 (4)
C16—N12	1.151 (4)	C42—C43	1.390 (4)
N21—C21	1.338 (3)	C42—C46	1.447 (4)
N21—C25	1.346 (3)	C43—H43	0.9500
C21—H21	0.9500	C43—C44	1.386 (4)
C21—C22	1.396 (3)	C44—H44	0.9500
C22—C23	1.395 (3)	C44—C45	1.385 (4)
C22—C26	1.438 (3)	C45—H45	0.9500
C23—H23	0.9500	C46—N42	1.141 (4)
N1—Fe1—N2	179.21 (9)	C24—C23—C22	117.7 (2)
N1—Fe1—N11	90.70 (8)	C24—C23—H23	121.1
N1—Fe1—N21	90.56 (8)	C23—C24—H24	120.3
N1—Fe1—N31	91.05 (8)	C23—C24—C25	119.4 (2)
N1—Fe1—N41	90.15 (9)	C25—C24—H24	120.3
N2—Fe1—N11	88.70 (8)	N21—C25—C24	123.3 (2)
N2—Fe1—N21	89.00 (8)	N21—C25—H25	118.4
N2—Fe1—N31	89.57 (8)	C24—C25—H25	118.4
N2—Fe1—N41	90.37 (8)	N22—C26—C22	177.9 (3)
N11—Fe1—N21	97.44 (7)	C31—N31—Fe1	122.38 (17)
N31—Fe1—N11	176.72 (7)	C31—N31—C35	118.0 (2)
N31—Fe1—N21	85.31 (7)	C35—N31—Fe1	119.59 (17)
N41—Fe1—N11	90.12 (7)	N31—C31—H31	118.8
N41—Fe1—N21	172.40 (7)	N31—C31—C32	122.3 (2)
N41—Fe1—N31	87.11 (7)	C32—C31—H31	118.8
Fe1—N1—C1	175.0 (2)	C31—C32—C33	119.6 (2)
N1—C1—S1	179.7 (3)	C31—C32—C36	119.4 (3)
Fe1—N2—C2	163.2 (2)	C33—C32—C36	121.0 (2)
N2—C2—S2	178.6 (2)	C32—C33—H33	121.0
C11—N11—Fe1	121.06 (16)	C34—C33—C32	118.0 (2)
C11—N11—C15	117.6 (2)	C34—C33—H33	121.0
C15—N11—Fe1	121.22 (16)	C33—C34—H34	120.5
N11—C11—H11	118.6	C33—C34—C35	119.1 (3)
N11—C11—C12	122.7 (2)	C35—C34—H34	120.5
C12—C11—H11	118.6	N31—C35—C34	122.9 (3)
C11—C12—C16	120.3 (2)	N31—C35—H35	118.5
C13—C12—C11	119.2 (2)	C34—C35—H35	118.5
C13—C12—C16	120.5 (2)	N32—C36—C32	179.0 (3)
C12—C13—H13	120.9	C41—N41—Fe1	123.72 (16)
C14—C13—C12	118.2 (2)	C41—N41—C45	117.8 (2)
C14—C13—H13	120.9	C45—N41—Fe1	118.22 (16)
C13—C14—H14	120.4	N41—C41—H41	118.8
C13—C14—C15	119.1 (2)	N41—C41—C42	122.3 (2)
C15—C14—H14	120.4	C42—C41—H41	118.8
N11—C15—C14	123.1 (2)	C41—C42—C46	119.7 (2)
N11—C15—H15	118.4	C43—C42—C41	119.7 (2)
C14—C15—H15	118.4	C43—C42—C46	120.5 (2)
N12—C16—C12	177.8 (3)	C42—C43—H43	121.1
C21—N21—Fe1	121.22 (16)	C44—C43—C42	117.8 (2)
C21—N21—C25	117.4 (2)	C44—C43—H43	121.1
C25—N21—Fe1	121.28 (17)	C43—C44—H44	120.4
N21—C21—H21	118.6	C45—C44—C43	119.2 (2)
N21—C21—C22	122.7 (2)	C45—C44—H44	120.4
C22—C21—H21	118.6	N41—C45—C44	123.2 (2)
C21—C22—C26	119.5 (2)	N41—C45—H45	118.4
C23—C22—C21	119.5 (2)	C44—C45—H45	118.4
C23—C22—C26	121.0 (2)	N42—C46—C42	179.7 (3)
C22—C23—H23	121.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N1	0.95	2.63	3.190 (3)	118
C15—H15···N2	0.95	2.58	3.113 (3)	115
C21—H21···N2	0.95	2.54	3.108 (3)	118
C24—H24···N22^i	0.95	2.67	3.514 (4)	148
C25—H25···N1	0.95	2.61	3.181 (3)	119
C31—H31···N1	0.95	2.67	3.214 (3)	117
C35—H35···N2	0.95	2.53	3.091 (3)	118
C35—H35···N12^ii	0.95	2.67	3.538 (4)	151
C41—H41···N22^iii	0.95	2.61	3.487 (3)	154
C44—H44···S1^iv	0.95	2.82	3.498 (3)	129
C45—H45···N2	0.95	2.55	3.123 (3)	119

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

Diaquabis(pyridine-3-carbonitrile)dithiocyanatoiron(II) pyridine-3-carbonitrile monosolvate (2)

Crystal data

[Fe(NCS)2(C6H4N2)2(H2O)2]·2C6H4N2	Z = 1
Mr = 624.49	F(000) = 320
Triclinic, P1	Dx = 1.463 Mg m^−3
a = 8.1065 (1) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.2880 (1) Å	Cell parameters from 25131 reflections
c = 11.4347 (2) Å	θ = 4.0–79.7°
α = 84.765 (1)°	µ = 6.01 mm^−1
β = 77.787 (1)°	T = 100 K
γ = 70.826 (1)°	Block, yellow
V = 709.02 (2) Å^3	0.11 × 0.10 × 0.08 mm

Data collection

XtaLAB Synergy, Dualflex, HyPix diffractometer	2999 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2999 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.022
Detector resolution: 10.0000 pixels mm^-1	θmax = 80.4°, θmin = 4.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysalisPro; Rigaku OD, 2023)	k = −10→10
Tmin = 0.727, Tmax = 1.000	l = −11→14
29397 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 0.2457P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max = 0.001
S = 1.15	Δρmax = 0.29 e Å^−3
2999 reflections	Δρmin = −0.24 e Å^−3
196 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0036 (4)
Primary atom site location: dual

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.

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

	x	y	z	Uiso*/Ueq
Fe1	0.500000	0.500000	0.500000	0.01216 (8)
N1	0.23749 (14)	0.50517 (14)	0.58058 (10)	0.0175 (2)
C1	0.10930 (16)	0.48617 (15)	0.64015 (11)	0.0145 (2)
S1	−0.06651 (4)	0.45890 (4)	0.72985 (3)	0.01772 (9)
O1	0.58744 (12)	0.38660 (11)	0.65983 (8)	0.01684 (18)
N11	0.55002 (13)	0.24567 (12)	0.42347 (9)	0.0137 (2)
C11	0.41230 (15)	0.20838 (15)	0.39913 (10)	0.0144 (2)
H11	0.295430	0.284514	0.423936	0.017*
C12	0.43436 (16)	0.06162 (15)	0.33861 (11)	0.0151 (2)
C13	0.60473 (17)	−0.05288 (15)	0.30294 (11)	0.0179 (2)
H13	0.622799	−0.154127	0.262362	0.022*
C14	0.74656 (16)	−0.01402 (16)	0.32865 (12)	0.0183 (2)
H14	0.864668	−0.088837	0.306060	0.022*
C15	0.71430 (16)	0.13553 (15)	0.38781 (11)	0.0163 (2)
H15	0.812998	0.161414	0.403931	0.020*
C16	0.27896 (17)	0.03358 (16)	0.31361 (12)	0.0195 (3)
N12	0.15470 (16)	0.01357 (16)	0.29369 (12)	0.0292 (3)
N21	0.40361 (14)	0.59653 (13)	0.85071 (9)	0.0177 (2)
C21	0.22852 (17)	0.62145 (16)	0.88138 (11)	0.0176 (2)
H21	0.176535	0.564393	0.838477	0.021*
C22	0.11976 (16)	0.72784 (15)	0.97378 (11)	0.0160 (2)
C23	0.19423 (17)	0.81232 (16)	1.03776 (11)	0.0177 (2)
H23	0.122870	0.885180	1.101462	0.021*
C24	0.37532 (17)	0.78663 (16)	1.00549 (12)	0.0190 (3)
H24	0.430907	0.842236	1.046636	0.023*
C25	0.47433 (16)	0.67873 (16)	0.91238 (11)	0.0177 (2)
H25	0.598501	0.661992	0.891042	0.021*
C26	−0.06797 (17)	0.74885 (16)	1.00254 (11)	0.0191 (3)
N22	−0.21762 (15)	0.76797 (16)	1.02557 (11)	0.0256 (3)
H1A	0.531 (3)	0.450 (3)	0.724 (2)	0.045 (6)*
H1B	0.693 (3)	0.369 (3)	0.6554 (18)	0.042 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01011 (13)	0.01477 (14)	0.01245 (14)	−0.00513 (10)	−0.00059 (9)	−0.00395 (9)
N1	0.0134 (5)	0.0216 (5)	0.0188 (5)	−0.0079 (4)	0.0004 (4)	−0.0065 (4)
C1	0.0146 (5)	0.0146 (5)	0.0155 (6)	−0.0034 (4)	−0.0054 (4)	−0.0043 (4)
S1	0.01226 (14)	0.02427 (16)	0.01741 (16)	−0.00805 (11)	−0.00037 (10)	−0.00184 (11)
O1	0.0146 (4)	0.0193 (4)	0.0166 (4)	−0.0046 (3)	−0.0025 (3)	−0.0045 (3)
N11	0.0132 (5)	0.0148 (5)	0.0131 (5)	−0.0048 (4)	−0.0013 (4)	−0.0020 (4)
C11	0.0134 (5)	0.0162 (5)	0.0137 (6)	−0.0048 (4)	−0.0023 (4)	−0.0018 (4)
C12	0.0159 (6)	0.0173 (5)	0.0141 (6)	−0.0077 (5)	−0.0025 (4)	−0.0018 (4)
C13	0.0188 (6)	0.0160 (6)	0.0190 (6)	−0.0064 (5)	−0.0004 (5)	−0.0046 (5)
C14	0.0141 (5)	0.0161 (6)	0.0223 (6)	−0.0029 (4)	0.0000 (5)	−0.0038 (5)
C15	0.0132 (5)	0.0192 (6)	0.0172 (6)	−0.0066 (5)	−0.0019 (4)	−0.0013 (5)
C16	0.0188 (6)	0.0182 (6)	0.0217 (6)	−0.0058 (5)	−0.0019 (5)	−0.0074 (5)
N12	0.0209 (6)	0.0302 (6)	0.0397 (7)	−0.0088 (5)	−0.0059 (5)	−0.0151 (5)
N21	0.0180 (5)	0.0207 (5)	0.0139 (5)	−0.0057 (4)	−0.0024 (4)	−0.0019 (4)
C21	0.0191 (6)	0.0207 (6)	0.0153 (6)	−0.0084 (5)	−0.0041 (5)	−0.0019 (5)
C22	0.0152 (6)	0.0189 (6)	0.0152 (6)	−0.0073 (5)	−0.0034 (4)	0.0005 (4)
C23	0.0181 (6)	0.0193 (6)	0.0162 (6)	−0.0068 (5)	−0.0015 (5)	−0.0040 (5)
C24	0.0183 (6)	0.0225 (6)	0.0194 (6)	−0.0097 (5)	−0.0045 (5)	−0.0029 (5)
C25	0.0147 (5)	0.0213 (6)	0.0172 (6)	−0.0066 (5)	−0.0026 (4)	0.0006 (5)
C26	0.0198 (6)	0.0216 (6)	0.0180 (6)	−0.0084 (5)	−0.0037 (5)	−0.0031 (5)
N22	0.0188 (6)	0.0314 (6)	0.0290 (6)	−0.0103 (5)	−0.0041 (5)	−0.0055 (5)

Geometric parameters (Å, º)

Fe1—N1^i	2.1207 (10)	C13—C14	1.3841 (17)
Fe1—N1	2.1207 (10)	C14—H14	0.9500
Fe1—O1^i	2.1267 (9)	C14—C15	1.3883 (17)
Fe1—O1	2.1267 (9)	C15—H15	0.9500
Fe1—N11	2.2358 (10)	C16—N12	1.1435 (18)
Fe1—N11^i	2.2358 (10)	N21—C21	1.3380 (16)
N1—C1	1.1649 (17)	N21—C25	1.3436 (16)
C1—S1	1.6387 (12)	C21—H21	0.9500
O1—H1A	0.89 (2)	C21—C22	1.3916 (18)
O1—H1B	0.81 (2)	C22—C23	1.3956 (17)
N11—C11	1.3390 (15)	C22—C26	1.4419 (17)
N11—C15	1.3463 (15)	C23—H23	0.9500
C11—H11	0.9500	C23—C24	1.3844 (17)
C11—C12	1.3960 (16)	C24—H24	0.9500
C12—C13	1.3949 (17)	C24—C25	1.3850 (18)
C12—C16	1.4421 (17)	C25—H25	0.9500
C13—H13	0.9500	C26—N22	1.1456 (17)
N1^i—Fe1—N1	180.0	C13—C12—C16	121.70 (11)
N1—Fe1—O1	89.42 (4)	C12—C13—H13	121.1
N1^i—Fe1—O1	90.58 (4)	C14—C13—C12	117.77 (11)
N1—Fe1—O1^i	90.58 (4)	C14—C13—H13	121.1
N1^i—Fe1—O1^i	89.42 (4)	C13—C14—H14	120.4
N1—Fe1—N11	89.86 (4)	C13—C14—C15	119.26 (11)
N1^i—Fe1—N11	90.14 (4)	C15—C14—H14	120.4
N1^i—Fe1—N11^i	89.86 (4)	N11—C15—C14	123.23 (11)
N1—Fe1—N11^i	90.14 (4)	N11—C15—H15	118.4
O1^i—Fe1—O1	180.0	C14—C15—H15	118.4
O1^i—Fe1—N11	87.62 (3)	N12—C16—C12	179.12 (14)
O1^i—Fe1—N11^i	92.38 (3)	C21—N21—C25	117.81 (11)
O1—Fe1—N11	92.38 (3)	N21—C21—H21	118.8
O1—Fe1—N11^i	87.62 (3)	N21—C21—C22	122.43 (11)
N11—Fe1—N11^i	180.0	C22—C21—H21	118.8
Fe1—N1—C1	167.09 (10)	C21—C22—C23	119.45 (11)
N1—C1—S1	177.12 (11)	C21—C22—C26	119.67 (11)
Fe1—O1—H1A	113.2 (14)	C23—C22—C26	120.87 (11)
Fe1—O1—H1B	112.3 (14)	C22—C23—H23	121.0
H1A—O1—H1B	106.9 (19)	C24—C23—C22	117.93 (12)
C11—N11—Fe1	118.64 (8)	C24—C23—H23	121.0
C11—N11—C15	117.74 (10)	C23—C24—H24	120.5
C15—N11—Fe1	123.18 (8)	C23—C24—C25	119.07 (11)
N11—C11—H11	118.8	C25—C24—H24	120.5
N11—C11—C12	122.34 (11)	N21—C25—C24	123.30 (11)
C12—C11—H11	118.8	N21—C25—H25	118.3
C11—C12—C16	118.64 (11)	C24—C25—H25	118.3
C13—C12—C11	119.66 (11)	N22—C26—C22	179.03 (14)
Fe1—N11—C11—C12	172.36 (9)	C16—C12—C13—C14	178.74 (12)
Fe1—N11—C15—C14	−172.87 (9)	N21—C21—C22—C23	−0.10 (19)
N11—C11—C12—C13	0.88 (18)	N21—C21—C22—C26	−179.84 (11)
N11—C11—C12—C16	−178.52 (11)	C21—N21—C25—C24	0.17 (18)
C11—N11—C15—C14	−0.63 (18)	C21—C22—C23—C24	0.31 (18)
C11—C12—C13—C14	−0.64 (18)	C22—C23—C24—C25	−0.28 (19)
C12—C13—C14—C15	−0.17 (18)	C23—C24—C25—N21	0.04 (19)
C13—C14—C15—N11	0.84 (19)	C25—N21—C21—C22	−0.14 (18)
C15—N11—C11—C12	−0.24 (17)	C26—C22—C23—C24	−179.96 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N21	0.89 (2)	1.88 (2)	2.7615 (14)	175 (2)
O1—H1B···S1^ii	0.81 (2)	2.62 (2)	3.3184 (9)	145.7 (18)
C11—H11···N1	0.95	2.54	3.1243 (16)	120
C11—H11···S1^iii	0.95	3.03	3.6833 (12)	128
C14—H14···S1^iv	0.95	2.98	3.7688 (13)	141
C15—H15···N1^i	0.95	2.67	3.1894 (16)	115
C21—H21···S1	0.95	2.92	3.8513 (13)	165
C24—H24···N22^ii	0.95	2.67	3.3082 (17)	125
C25—H25···S1^ii	0.95	3.01	3.8056 (13)	142

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