The structures and phase transitions in 4-amino­pyridinium tetra­aqua­bis­(sulfato)­iron(III), (C₅H₇N₂)[Fe^III(H₂O)₄(SO₄)₂]

The organic–inorganic hybrid compound 4-amino­pyridinium tetra­aqua­bis­(sulfato)­iron(III), (C₅H₇N₂)[Fe^III(H₂O)₄(SO₄)₂] (4apFeS), was obtained by slow evaporation of the solvent at room temperature and characterized by single-crystal X-ray diffraction in the temperature range from 290 to 80 K. Differential scanning calorimetry revealed that the title compound undergoes a sequence of three reversible phase transitions, which has been verified by variable-temperature X-ray diffraction analysis during cooling–heating cycles over the temperature ranges 290–100–290 K. In the room-temperature phase (I), space group C2/c, oxygen atoms from the closest Fe-atom environment (octahedral) were disordered over two equivalent positions around a twofold axis. Two intermediate phases (II), (III) were solved and refined as incommensurately modulated structures, employing the superspace formalism applied to single-crystal X-ray diffraction data. Both structures can be described in the (3+1)-dimensional monoclinic X2/c(α,0,γ)0s superspace group (where X is ½, ½, 0, ½) with modulation wavevectors q = (0.2943, 0, 0.5640) and q = (0.3366, 0, 0.5544) for phases (II) and (III), respectively. The completely ordered low-temperature phase (IV) was refined with the twinning model in the triclinic P space group, revealing the existence of two domains. The dynamics of the disordered anionic substructure in the 4apFeS crystal seems to play an essential role in the phase transition mechanisms. The discrete organic moieties were found to be fully ordered even at room temperature.

Computing details

Data collection: CrysAlis PRO 1.171.39.12b (Rigaku OD, 2015) for PhaseII, PhaseIII; CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for PhaseIV. Cell refinement: CrysAlis PRO 1.171.39.12b (Rigaku OD, 2015) for PhaseII, PhaseIII; CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for PhaseIV. Data reduction: CrysAlis PRO 1.171.39.12b (Rigaku OD, 2015) for PhaseII, PhaseIII; CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for PhaseIV. Program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2015) for PhaseIV. Program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015) for PhaseIV. Molecular graphics: Diamond 2.1c (Brandenburg, 1997) for PhaseIV. Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for PhaseIV.

(PhaseII)

Crystal data

FeS2O12N2C5H15	Z = 4
Mr = 415.1	F(000) = 852
Monoclinic, X2/c(α0γ)0s†	Dx = 1.974 Mg m^−3
q = 0.294300a* + 0.564000c*	Mo Kα radiation, λ = 0.71073 Å
a = 12.1601 (3) Å	Cell parameters from 6734 reflections
b = 17.2511 (3) Å	θ = 3.4–29.3°
c = 6.7758 (2) Å	µ = 1.45 mm^−1
β = 100.715 (2)°	T = 245 K
V = 1396.61 (6) Å^3	0.51 × 0.44 × 0.30 mm

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂, −x₃+1/2, −x₄+1/2; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁, −x₂, x₃+1/2, x₄+1/2; (5) x₁+1/2, x₂+1/2, x₃, x₄+1/2; (6) −x₁+1/2, x₂+1/2, −x₃+1/2, −x₄; (7) −x₁+1/2, −x₂+1/2, −x₃, −x₄+1/2; (8) x₁+1/2, −x₂+1/2, x₃+1/2, x₄.

Data collection

Xcalibur, Atlas diffractometer	5303 independent reflections
Radiation source: X-ray tube	2856 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.6°, θmin = 3.0°
ω scans	h = −16→17
Absorption correction: analytical CrysAlisPro 1.171.39.12b (Rigaku Oxford Diffraction, 2015) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −23→22
Tmin = 0.586, Tmax = 0.751	l = −9→9
23230 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
wR(F^2) = 0.089	(Δ/σ)max = 3.804
S = 1.34	Δρmax = 1.24 e Å^−3
5303 reflections	Δρmin = −0.61 e Å^−3
384 parameters	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 5408.21
41 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.5	0.356897 (15)	0.25	0.01310 (9)
S1	0.33286 (3)	0.351013 (19)	−0.19593 (5)	0.01402 (11)
O2s	0.22908 (8)	0.34282 (6)	−0.11998 (17)	0.0264 (4)
O4s	0.33393 (13)	0.42245 (6)	−0.3114 (2)	0.0277 (4)
O3s	0.35027 (13)	0.28467 (7)	−0.3189 (2)	0.0258 (7)
O6w	0.6044 (2)	0.27668 (14)	0.1791 (4)	0.0317 (9)
O5w1	0.5921 (7)	0.4411 (3)	0.1541 (10)	0.0516 (12)	0.5
O5w2	0.6067 (6)	0.4360 (3)	0.1756 (8)	0.0213 (10)	0.5
N1	0.5	0.08806 (12)	0.25	0.0280 (8)
O1b1	0.4271 (5)	0.3484 (4)	−0.0265 (8)	0.0204 (8)	0.5
O1b2	0.4281 (5)	0.3630 (5)	−0.0241 (8)	0.045 (2)	0.5
N2	0.5	−0.14851 (10)	0.25	0.0282 (7)
C1	0.5	0.01091 (12)	0.25	0.0200 (6)
C2	0.39963 (12)	−0.03151 (9)	0.2237 (2)	0.0267 (5)
C3	0.40199 (13)	−0.11030 (9)	0.2261 (2)	0.0294 (5)
H1c2	0.329214	−0.00477	0.204043	0.032*
H1c3	0.333185	−0.138886	0.21059	0.0352*
H1n1	0.544 (5)	0.108 (3)	0.293 (7)	0.033620 (2)*	0.5
H2n1	0.559 (5)	0.113 (3)	0.242 (7)	0.033620 (2)*	0.5
H1n2	0.5	−0.198938	0.25	0.0338*
H1o6w	0.6228 (18)	0.2806 (12)	0.069 (4)	0.016 (9)*
H2o6w	0.642 (3)	0.2512 (15)	0.243 (5)	0.000 (8)*
H1o5w1	0.605 (3)	0.436 (2)	0.094 (6)	−0.030 (6)*	0.5
H2o5w1	0.629 (3)	0.508 (3)	0.239 (6)	−0.010 (8)*	0.5
H1o5w2	0.631 (2)	0.437 (2)	0.123 (7)	−0.012 (7)*	0.5
H2o5w2	0.630 (3)	0.515 (3)	0.239 (5)	−0.001 (8)*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01362 (15)	0.01408 (15)	0.01110 (16)	0	0.00098 (12)	0
S1	0.01275 (17)	0.01712 (18)	0.01179 (19)	0.00005 (12)	0.00129 (14)	0.00043 (12)
O2s	0.0172 (5)	0.0314 (6)	0.0327 (7)	−0.0009 (4)	0.0106 (5)	0.0004 (5)
O4s	0.0431 (7)	0.0153 (5)	0.0270 (7)	−0.0005 (5)	0.0128 (6)	0.0016 (5)
O3s	0.0422 (12)	0.0150 (9)	0.0232 (15)	0.0015 (8)	0.0137 (10)	−0.0003 (10)
O6w	0.0359 (15)	0.0348 (15)	0.0279 (15)	0.0201 (10)	0.0147 (12)	0.0082 (9)
O5w1	0.094 (2)	0.0295 (19)	0.0460 (15)	−0.0328 (19)	0.0502 (16)	−0.0181 (14)
O5w2	0.0245 (19)	0.0222 (14)	0.0176 (18)	−0.0090 (12)	0.0046 (13)	−0.0011 (11)
N1	0.0214 (12)	0.0180 (10)	0.0435 (15)	0	0.0032 (11)	0
O1b1	0.0235 (9)	0.019 (2)	0.0152 (9)	0.0029 (16)	−0.0046 (7)	−0.0039 (15)
O1b2	0.019 (2)	0.101 (6)	0.0140 (15)	0.001 (3)	−0.0031 (12)	0.005 (2)
N2	0.0348 (11)	0.0140 (9)	0.0336 (12)	0	0.0009 (10)	0
C1	0.0206 (10)	0.0192 (10)	0.0204 (11)	0	0.0040 (9)	0
C2	0.0171 (7)	0.0241 (8)	0.0379 (10)	0.0008 (6)	0.0026 (7)	−0.0008 (7)
C3	0.0232 (8)	0.0260 (8)	0.0378 (10)	−0.0061 (7)	0.0027 (7)	−0.0011 (7)

Geometric parameters (Å, º)

	Average	Minimum	Maximum
Fe1—O6w	2.00 (2)	1.94 (3)	2.04 (3)
Fe1—O6w^i	2.00 (2)	1.93 (3)	2.04 (3)
Fe1—O5w1	2.01 (4)	1.98 (6)	2.02 (6)
Fe1—O5w1^i	2.01 (4)	1.98 (6)	2.02 (6)
Fe1—O5w2	2.033 (17)	1.997 (18)	2.074 (18)
Fe1—O5w2^i	2.032 (17)	1.996 (18)	2.070 (18)
Fe1—O1b1	1.946 (8)	1.914 (8)	2.001 (8)
Fe1—O1b1^i	1.947 (8)	1.914 (8)	1.998 (8)
Fe1—O1b2	1.917 (18)	1.90 (3)	1.93 (3)
Fe1—O1b2^i	1.917 (18)	1.90 (3)	1.93 (3)
Fe1—H1o5w1	2.33 (10)	1.73 (10)	2.68 (10)
Fe1—H1o5w1^i	2.32 (10)	1.76 (10)	2.68 (10)
S1—O2s	1.4568 (18)	1.4550 (18)	1.4594 (18)
S1—O4s	1.468 (2)	1.459 (2)	1.481 (2)
S1—O3s	1.46 (2)	1.45 (3)	1.48 (3)
S1—O1b1	1.506 (8)	1.476 (8)	1.582 (8)
S1—O1b2	1.486 (18)	1.48 (3)	1.51 (3)
S1—H2o5w1^ii	2.50 (12)	1.36 (13)	3.05 (13)
S1—H2o5w2^ii	2.49 (13)	1.07 (15)	3.18 (15)
O4s—H2o5w1^ii	1.46 (11)	0.11 (13)	2.10 (13)
O4s—H2o5w2^ii	1.34 (13)	0.11 (15)	1.97 (15)
O6w—H1o6w	0.84 (13)	0.43 (16)	1.25 (16)
O6w—H2o6w	0.72 (8)	0.13 (10)	1.41 (10)
O5w1—H1o5w1	0.73 (11)	0.37 (12)	1.07 (12)
O5w1—H2o5w1	1.35 (12)	0.59 (13)	3.56 (13)
O5w2—H1o5w1	0.59 (10)	0.53 (10)	0.65 (10)
O5w2—H1o5w2	0.83 (11)	0.46 (12)	1.20 (12)
O5w2—H2o5w2	1.40 (13)	0.66 (15)	3.36 (15)
N1—C1	1.331 (3)	1.330 (4)	1.332 (4)
N1—H1n1	0.66 (6)	0.65 (6)	0.66 (6)
N1—H1n1^i	0.66 (6)	0.65 (6)	0.66 (6)
N1—H2n1	0.85 (6)	0.85 (6)	0.85 (6)
N1—H2n1^i	0.85 (6)	0.85 (6)	0.85 (6)
N2—C3	1.345 (3)	1.344 (3)	1.346 (3)
N2—C3^i	1.345 (3)	1.344 (3)	1.346 (3)
N2—H1n2	0.9 (17)	0.9 (17)	0.9 (17)
C1—C2	1.406 (3)	1.404 (3)	1.408 (3)
C1—C2^i	1.406 (3)	1.404 (3)	1.408 (3)
C2—C3	1.360 (3)	1.358 (3)	1.361 (3)
C2—H1c2	1.0 (13)	1.0 (13)	1.0 (13)
C3—H1c3	1.0 (14)	1.0 (14)	1.0 (14)
H1n1—H2n1	0.43 (8)	0.43 (8)	0.44 (8)
H1o5w1—H2o5w1	1.68 (15)	0.89 (16)	3.41 (16)
H1o5w2—H2o5w2	1.52 (16)	0.93 (18)	2.20 (18)
O6w—Fe1—O6w^i	91.9 (10)	88.6 (9)	94.4 (9)
O6w—Fe1—O5w1	88.9 (9)	85.9 (8)	91.1 (9)
O6w—Fe1—O5w1^i	175.9 (8)	171.5 (7)	178.9 (9)
O6w—Fe1—O5w2	88.9 (9)	87.4 (8)	96.0 (8)
O6w—Fe1—O5w2^i	176.2 (8)	168.0 (7)	178.3 (8)
O6w—Fe1—O1b1	86.8 (7)	81.4 (6)	100.2 (6)
O6w—Fe1—O1b1^i	90.9 (7)	83.2 (6)	101.5 (6)
O6w—Fe1—O1b2	88.4 (7)	82.3 (6)	97.0 (6)
O6w—Fe1—O1b2^i	92.1 (7)	88.3 (6)	98.1 (6)
O6w—Fe1—H1o5w1	83 (2)	76 (2)	108 (3)
O6w—Fe1—H1o5w1^i	164 (2)	156 (2)	172 (2)
O6w^i—Fe1—O5w1	175.9 (8)	171.6 (7)	178.9 (9)
O6w^i—Fe1—O5w1^i	88.8 (9)	85.9 (8)	91.1 (9)
O6w^i—Fe1—O5w2	176.1 (8)	167.6 (7)	178.4 (9)
O6w^i—Fe1—O5w2^i	88.9 (9)	87.4 (9)	95.7 (8)
O6w^i—Fe1—O1b1	90.9 (7)	83.4 (6)	101.6 (6)
O6w^i—Fe1—O1b1^i	86.8 (7)	81.4 (6)	100.0 (6)
O6w^i—Fe1—O1b2	92.1 (7)	88.3 (7)	98.1 (6)
O6w^i—Fe1—O1b2^i	88.4 (7)	82.3 (6)	97.0 (6)
O6w^i—Fe1—H1o5w1	164 (2)	156 (2)	172 (2)
O6w^i—Fe1—H1o5w1^i	83 (2)	76 (2)	105 (3)
O5w1—Fe1—O5w1^i	88.6 (10)	88.1 (8)	89.7 (14)
O5w1—Fe1—O5w2^i	93.5 (16)	91.7 (12)	94.5 (15)
O5w1—Fe1—O1b1	86.1 (10)	73.0 (13)	91.4 (13)
O5w1—Fe1—O1b1^i	95.3 (8)	85.6 (9)	104.1 (13)
O5w1—Fe1—O1b2^i	92.9 (13)	86.5 (10)	101.0 (13)
O5w1—Fe1—H1o5w1	16 (2)	10 (2)	21 (3)
O5w1^i—Fe1—O5w2	93.6 (16)	91.8 (12)	94.5 (15)
O5w1^i—Fe1—O1b1	95.3 (8)	85.4 (9)	104.0 (13)
O5w1^i—Fe1—O1b1^i	86.1 (10)	73.1 (13)	91.4 (13)
O5w1^i—Fe1—O1b2	93.1 (13)	86.6 (10)	101.2 (13)
O5w1^i—Fe1—H1o5w1^i	16 (2)	10 (2)	21 (2)
O5w2—Fe1—O5w2^i	88.3 (7)	84.6 (7)	90.4 (7)
O5w2—Fe1—O1b1^i	97.2 (5)	96.4 (5)	99.1 (5)
O5w2—Fe1—O1b2	85.0 (5)	71.7 (5)	89.6 (5)
O5w2—Fe1—O1b2^i	95.4 (5)	85.6 (5)	107.0 (5)
O5w2—Fe1—H1o5w1^i	92 (2)	75 (3)	102.2 (19)
O5w2^i—Fe1—O1b1	97.2 (5)	96.5 (5)	98.9 (5)
O5w2^i—Fe1—O1b2	95.1 (5)	85.6 (5)	106.8 (5)
O5w2^i—Fe1—O1b2^i	85.1 (5)	72.0 (5)	89.6 (5)
O5w2^i—Fe1—H1o5w1	92 (2)	73 (3)	102.4 (19)
O1b1—Fe1—O1b1^i	177.0 (4)	175.2 (4)	178.1 (4)
O1b1—Fe1—O1b2^i	172.0 (5)	164.7 (5)	175.7 (4)
O1b1—Fe1—H1o5w1	78 (2)	72.3 (19)	95 (3)
O1b1^i—Fe1—O1b2	171.8 (5)	164.3 (5)	175.7 (4)
O1b1^i—Fe1—H1o5w1^i	78 (2)	72.3 (19)	93 (3)
O1b2—Fe1—O1b2^i	175.9 (9)	174.6 (11)	177.7 (11)
O1b2—Fe1—H1o5w1^i	103 (2)	99 (3)	104 (2)
O1b2^i—Fe1—H1o5w1	103 (3)	98 (3)	104 (2)
O2s—S1—O4s	111.36 (12)	111.02 (12)	111.62 (12)
O2s—S1—O3s	110.5 (9)	107.3 (9)	112.6 (9)
O2s—S1—O1b1	109.6 (4)	107.1 (4)	110.6 (3)
O2s—S1—O1b2	108.9 (4)	105.2 (4)	111.6 (4)
O2s—S1—H2o5w1^ii	110 (3)	101 (4)	113 (2)
O2s—S1—H2o5w2^ii	108 (2)	104.9 (18)	114 (4)
O4s—S1—O3s	110.1 (9)	102.6 (8)	117.5 (8)
O4s—S1—O1b1	108.0 (4)	95.7 (4)	117.8 (4)
O4s—S1—O1b2	105.7 (5)	95.8 (5)	111.3 (5)
O4s—S1—H2o5w1^ii	29 (2)	3(4)	39.2 (16)
O4s—S1—H2o5w2^ii	22 (2)	3(4)	39 (6)
O3s—S1—O1b1	107.5 (9)	100.9 (8)	124.9 (11)
O3s—S1—O1b2	109.1 (9)	100.4 (9)	123.0 (11)
O3s—S1—H2o5w1^ii	127 (3)	86 (5)	141 (2)
O3s—S1—H2o5w2^ii	125 (3)	70 (6)	135 (2)
O1b1—S1—H2o5w2^ii	97 (2)	92.0 (16)	131 (5)
O1b2—S1—H2o5w1^ii	85 (2)	69.4 (19)	132 (4)
H2o5w1^ii—S1—H2o5w2^ii	58 (6)	48 (6)	67 (6)
S1—O4s—H2o5w1^ii	115 (7)	67 (7)	140 (30)
S1—O4s—H2o5w2^ii	118 (7)	30 (30)	135 (3)
H2o5w1^ii—O4s—H2o5w2^ii	173 (7)	173 (6)	174 (7)
Fe1—O6w—H1o6w	117 (13)	108 (17)	130 (20)
Fe1—O6w—H2o6w	130 (12)	125 (5)	140 (40)
H1o6w—O6w—H2o6w	107 (17)	80 (11)	120 (11)
Fe1—O5w1—H1o5w1	106 (8)	59 (7)	118 (6)
Fe1—O5w1—H2o5w1	129 (7)	124 (6)	133 (5)
H1o5w1—O5w1—H2o5w1	105 (12)	63 (11)	114 (12)
Fe1—O5w2—H1o5w1	69 (8)	68 (7)	70 (9)
Fe1—O5w2—H1o5w2	118 (7)	81 (4)	178 (13)
Fe1—O5w2—H2o5w2	129 (5)	124 (6)	134 (8)
H1o5w2—O5w2—H2o5w2	88 (9)	37 (9)	113 (10)
C1—N1—H1n1	122 (5)	122 (5)	123 (5)
C1—N1—H1n1^i	122 (5)	122 (5)	123 (5)
C1—N1—H2n1	121 (4)	120 (4)	121 (4)
C1—N1—H2n1^i	121 (4)	120 (4)	121 (4)
H1n1—N1—H1n1^i	116 (7)	115 (7)	117 (7)
H1n1—N1—H2n1	30 (6)	30 (5)	30 (6)
H1n1—N1—H2n1^i	109 (6)	108 (6)	110 (6)
H1n1^i—N1—H2n1	109 (6)	108 (6)	110 (6)
H1n1^i—N1—H2n1^i	30 (6)	30 (5)	30 (6)
H2n1—N1—H2n1^i	119 (5)	118 (5)	119 (5)
Fe1—O1b1—S1	148.2 (6)	134.8 (6)	155.9 (6)
Fe1—O1b2—S1	153.5 (15)	150 (2)	158 (2)
C3—N2—C3^i	121.3 (2)	121.3 (2)	121.3 (2)
C3—N2—H1n2	119.34	119.33	119.35
C3^i—N2—H1n2	119.34	119.33	119.35
N1—C1—C2	121.37 (17)	121.32 (14)	121.42 (14)
N1—C1—C2^i	121.37 (17)	121.32 (14)	121.42 (14)
C2—C1—C2^i	117.3 (2)	117.2 (3)	117.3 (3)
C1—C2—C3	120.2 (2)	120.1 (2)	120.3 (2)
C1—C2—H1c2	119.9	119.85	119.94
C3—C2—H1c2	119.9	119.85	119.94
N2—C3—C2	120.5 (2)	120.5 (2)	120.5 (2)
N2—C3—H1c3	119.75	119.73	119.77
C2—C3—H1c3	119.75	119.73	119.77
N1—H1n1—H2n1	101 (10)	100 (10)	101 (10)
N1—H2n1—H1n1	49 (9)	49 (9)	50 (9)
Fe1—H1o5w1—O5w1	58 (8)	42 (4)	101 (11)
Fe1—H1o5w1—O5w2	93 (10)	92 (9)	94 (11)
Fe1—H1o5w1—H2o5w1	96 (6)	68 (6)	148 (9)
O5w1—H1o5w1—H2o5w1	47 (9)	25 (5)	84 (13)
S1^ii—H2o5w1—O4s^ii	36 (7)	24 (2)	90 (17)
S1^ii—H2o5w1—O5w1	144 (8)	91 (5)	159 (10)
S1^ii—H2o5w1—H1o5w1	126 (7)	98 (5)	168 (9)
O4s^ii—H2o5w1—O5w1	151 (14)	16 (6)	179 (14)
O4s^ii—H2o5w1—H1o5w1	136 (12)	14 (8)	170 (11)
O5w1—H2o5w1—H1o5w1	28 (6)	8(2)	43 (8)
O5w2—H1o5w2—H2o5w2	59 (8)	27 (5)	132 (11)
S1^ii—H2o5w2—O4s^ii	41 (8)	19.0 (15)	150 (60)
S1^ii—H2o5w2—O5w2	151 (8)	101 (7)	162 (10)
S1^ii—H2o5w2—H1o5w2	131 (8)	119 (7)	156 (9)
O4s^ii—H2o5w2—O5w2	150 (14)	10 (7)	180 (11)
O4s^ii—H2o5w2—H1o5w2	142 (13)	30 (50)	159 (16)
O5w2—H2o5w2—H1o5w2	33 (5)	10 (2)	53 (8)

Symmetry codes: (i) −x₁+1, x₂, −x₃+1/2, −x₄+1/2; (ii) −x₁+1, −x₂+1, −x₃, −x₄.

(PhaseIII)

Crystal data

C5N2O12S2FeH15	Z = 4
Mr = 415.1	F(000) = 852
Monoclinic, X2/c(α0γ)0s†	Dx = 1.979 Mg m^−3
q = 0.336600a* + 0.554400c*	Mo Kα radiation, λ = 0.71073 Å
a = 12.175 (11) Å	Cell parameters from 7559 reflections
b = 17.217 (5) Å	θ = 3.4–29.3°
c = 6.769 (2) Å	µ = 1.45 mm^−1
β = 100.87 (4)°	T = 195 K
V = 1393.4 (14) Å^3	0.51 × 0.44 × 0.30 mm

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂, −x₃+1/2, −x₄+1/2; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁, −x₂, x₃+1/2, x₄+1/2; (5) x₁+1/2, x₂+1/2, x₃, x₄+1/2; (6) −x₁+1/2, x₂+1/2, −x₃+1/2, −x₄; (7) −x₁+1/2, −x₂+1/2, −x₃, −x₄+1/2; (8) x₁+1/2, −x₂+1/2, x₃+1/2, x₄.

Data collection

Xcalibur, Atlas diffractometer	5282 independent reflections
Radiation source: X-ray tube	3721 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.6°, θmin = 2.4°
ω scans	h = −17→16
Absorption correction: gaussian Jana2006	k = −23→22
Tmin = 0.583, Tmax = 0.752	l = −9→9
23241 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
wR(F^2) = 0.075	(Δ/σ)max = 0.047
S = 2.01	Δρmax = 0.76 e Å^−3
5282 reflections	Δρmin = −0.45 e Å^−3
343 parameters	Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
7 restraints	Extinction coefficient: 5320 (160)
105 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	1	0.643241 (12)	0.25	0.01092 (8)
S1	0.83288 (2)	0.649134 (15)	−0.19644 (4)	0.01169 (9)
O1b1	0.92703 (17)	0.66428 (13)	−0.0272 (3)	0.0292 (5)	0.5
O1b2	0.92889 (17)	0.62694 (10)	−0.0238 (3)	0.0236 (4)	0.5
O2s	0.72909 (7)	0.65734 (5)	−0.11977 (13)	0.0213 (3)
O3s	0.85049 (7)	0.71561 (5)	−0.31897 (12)	0.0227 (3)
O5w1	1.08154 (17)	0.55665 (9)	0.1413 (2)	0.0317 (5)	0.5
O5w2	1.11916 (17)	0.56749 (8)	0.1928 (2)	0.0214 (4)	0.5
O6w	1.10435 (9)	0.72361 (6)	0.17929 (15)	0.0239 (3)
O4s	0.83380 (9)	0.57748 (5)	−0.31196 (16)	0.0209 (6)
N1	0.5	0.41157 (8)	0.25	0.0222 (5)
N2	0.5	0.64870 (8)	0.25	0.0229 (5)
C1	0.5	0.48873 (9)	0.25	0.0170 (5)
C2	0.39927 (10)	0.53146 (7)	0.22442 (19)	0.0222 (4)
C3	0.40184 (10)	0.61031 (7)	0.22710 (19)	0.0245 (4)
H1c2	0.328874	0.504717	0.205097	0.0266*
H1c3	0.333164	0.638985	0.212572	0.0294*
H1n1	0.5581 (16)	0.3871 (16)	0.224 (4)	0.0267 (4)*	0.5
H2n1	0.4409 (15)	0.3878 (16)	0.186 (4)	0.0267 (4)*	0.5
H1n2	0.5	0.699228	0.25	0.0275*
H1o6w	1.1217 (12)	0.7187 (8)	0.0715 (13)	0.0287 (13)*
H1o5w1	1.1032 (17)	0.5621 (11)	0.0374 (18)	0.038033 (2)*	0.5
H2o5w1	1.1076 (15)	0.5181 (7)	0.198 (3)	0.038033 (2)*	0.5
H2o6w	1.1446 (10)	0.7517 (7)	0.2552 (16)	0.0287 (16)*
H1o5w2	1.1302 (16)	0.5700 (10)	0.0799 (14)	0.0256 (14)*	0.5
H2o5w2	1.1252 (15)	0.5231 (5)	0.228 (3)	0.0256 (3)*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01136 (12)	0.01141 (13)	0.00961 (14)	0	0.00097 (9)	0
S1	0.01085 (14)	0.01380 (15)	0.01008 (16)	−0.00005 (10)	0.00111 (11)	−0.00030 (10)
O1b1	0.0172 (7)	0.0541 (9)	0.0137 (7)	−0.0033 (8)	−0.0038 (5)	0.0035 (8)
O1b2	0.0168 (6)	0.0384 (8)	0.0130 (7)	0.0050 (7)	−0.0036 (5)	−0.0052 (7)
O2s	0.0145 (4)	0.0261 (5)	0.0250 (5)	0.0003 (3)	0.0079 (4)	−0.0006 (4)
O3s	0.0343 (5)	0.0140 (4)	0.0222 (5)	−0.0001 (4)	0.0118 (4)	0.0018 (3)
O5w1	0.0564 (11)	0.0190 (7)	0.0272 (8)	0.0183 (7)	0.0270 (8)	0.0088 (6)
O5w2	0.0288 (8)	0.0179 (7)	0.0201 (7)	0.0101 (6)	0.0113 (6)	0.0058 (5)
O6w	0.0289 (5)	0.0275 (5)	0.0174 (5)	−0.0162 (4)	0.0099 (4)	−0.0063 (4)
O4s	0.0318 (11)	0.0132 (7)	0.0190 (12)	0.0003 (7)	0.0080 (8)	−0.0010 (7)
N1	0.0172 (7)	0.0149 (7)	0.0334 (9)	0	0.0018 (7)	0
N2	0.0279 (8)	0.0120 (7)	0.0272 (9)	0	0.0009 (7)	0
C1	0.0172 (8)	0.0168 (8)	0.0167 (8)	0	0.0028 (7)	0
C2	0.0144 (5)	0.0201 (6)	0.0311 (7)	−0.0006 (5)	0.0023 (5)	−0.0001 (5)
C3	0.0201 (6)	0.0218 (6)	0.0304 (7)	0.0049 (5)	0.0020 (6)	0.0007 (5)

Geometric parameters (Å, º)

	Average	Minimum	Maximum
Fe1—O1b1	1.937 (6)	1.926 (9)	1.950 (9)
Fe1—O1b1^i	1.937 (6)	1.926 (9)	1.950 (9)
Fe1—O1b2	1.929 (6)	1.904 (9)	1.937 (9)
Fe1—O1b2^i	1.929 (6)	1.904 (9)	1.937 (9)
Fe1—O5w1	2.012 (7)	2.002 (10)	2.028 (10)
Fe1—O5w1^i	2.012 (7)	2.002 (10)	2.028 (10)
Fe1—O5w2	2.032 (7)	2.023 (11)	2.058 (11)
Fe1—O5w2^i	2.031 (7)	2.023 (11)	2.058 (11)
Fe1—O6w	2.007 (6)	1.979 (8)	2.036 (8)
Fe1—O6w^i	2.007 (6)	1.978 (8)	2.036 (8)
S1—O1b1	1.493 (6)	1.476 (9)	1.514 (9)
S1—O1b2	1.503 (6)	1.483 (8)	1.551 (8)
S1—O2s	1.462 (3)	1.460 (3)	1.465 (3)
S1—O3s	1.4612 (14)	1.4518 (14)	1.4746 (14)
S1—O4s	1.47 (2)	1.47 (3)	1.48 (3)
O5w1—H1o5w1	0.801 (18)	0.80 (2)	0.80 (2)
O5w1—H2o5w1	0.801 (16)	0.801 (18)	0.801 (18)
O5w2—H1o5w2	0.801 (14)	0.801 (16)	0.801 (16)
O5w2—H2o5w2	0.801 (11)	0.801 (12)	0.801 (12)
O6w—H1o6w	0.801 (12)	0.801 (12)	0.801 (12)
O6w—H2o6w	0.801 (13)	0.801 (13)	0.801 (13)
N1—C1	1.328 (3)	1.322 (3)	1.335 (3)
N1—H1n1	0.87 (2)	0.87 (2)	0.87 (2)
N1—H1n1^ii	0.87 (2)	0.87 (2)	0.87 (2)
N1—H2n1	0.87 (2)	0.86 (2)	0.88 (2)
N1—H2n1^ii	0.87 (2)	0.86 (2)	0.88 (2)
N2—C3	1.349 (3)	1.348 (3)	1.350 (3)
N2—C3^ii	1.349 (3)	1.348 (3)	1.350 (3)
N2—H1n2	0.9 (17)	0.9 (17)	0.9 (17)
C1—C2	1.413 (3)	1.410 (4)	1.416 (4)
C1—C2^ii	1.413 (3)	1.410 (4)	1.416 (4)
C2—C3	1.358 (3)	1.358 (3)	1.358 (3)
C2—H1c2	1.0 (13)	1.0 (13)	1.0 (13)
C3—H1c3	1.0 (14)	1.0 (14)	1.0 (14)
H1n1—H2n1^ii	0.61 (4)	0.60 (4)	0.61 (4)
O1b1—Fe1—O1b2^i	177.5 (2)	174.9 (3)	178.6 (3)
O1b1—Fe1—O5w1	87.5 (2)	87.09 (18)	88.6 (3)
O1b1—Fe1—O5w2^i	96.0 (2)	93.7 (3)	96.6 (2)
O1b1—Fe1—O6w	85.1 (2)	80.2 (3)	86.82 (14)
O1b1—Fe1—O6w^i	89.0 (2)	85.1 (3)	90.35 (13)
O1b1^i—Fe1—O1b2	177.5 (2)	174.9 (3)	178.6 (3)
O1b1^i—Fe1—O5w1^i	87.5 (2)	87.09 (18)	88.6 (3)
O1b1^i—Fe1—O5w2	96.0 (2)	93.7 (3)	96.6 (2)
O1b1^i—Fe1—O6w	89.0 (2)	85.1 (3)	90.35 (13)
O1b1^i—Fe1—O6w^i	85.1 (2)	80.2 (3)	86.82 (14)
O1b2—Fe1—O5w1^i	94.01 (19)	92.6 (2)	95.3 (2)
O1b2—Fe1—O5w2	85.87 (19)	85.01 (15)	88.1 (2)
O1b2—Fe1—O6w	89.6 (2)	88.7 (3)	91.4 (2)
O1b2—Fe1—O6w^i	93.0 (2)	91.7 (2)	96.3 (2)
O1b2^i—Fe1—O5w1	94.00 (19)	92.6 (2)	95.3 (2)
O1b2^i—Fe1—O5w2^i	85.85 (19)	85.01 (15)	88.1 (2)
O1b2^i—Fe1—O6w	92.9 (2)	91.7 (2)	96.3 (2)
O1b2^i—Fe1—O6w^i	89.5 (2)	88.7 (3)	91.4 (2)
O5w1—Fe1—O5w2^i	90.9 (2)	89.83 (13)	92.49 (13)
O5w1—Fe1—O6w	90.4 (3)	89.1 (3)	93.18 (18)
O5w1—Fe1—O6w^i	175.6 (2)	171.29 (15)	177.4 (2)
O5w1^i—Fe1—O5w2	90.9 (2)	89.83 (13)	92.48 (13)
O5w1^i—Fe1—O6w	175.5 (2)	171.30 (15)	177.4 (2)
O5w1^i—Fe1—O6w^i	90.4 (3)	89.1 (3)	93.19 (18)
O5w2—Fe1—O6w	86.8 (2)	82.13 (18)	88.7 (3)
O5w2—Fe1—O6w^i	177.10 (19)	173.04 (16)	178.60 (18)
O5w2^i—Fe1—O6w	177.09 (19)	173.01 (16)	178.60 (18)
O5w2^i—Fe1—O6w^i	86.9 (2)	82.11 (18)	88.7 (3)
O6w—Fe1—O6w^i	91.8 (2)	91.6 (2)	92.4 (3)
O1b1—S1—O2s	109.0 (3)	108.0 (3)	109.4 (4)
O1b1—S1—O3s	105.0 (3)	96.9 (3)	109.76 (19)
O1b1—S1—O4s	110.2 (9)	104.9 (8)	119.1 (9)
O1b2—S1—O2s	109.4 (3)	108.47 (18)	110.6 (3)
O1b2—S1—O3s	110.1 (2)	107.13 (15)	117.6 (3)
O1b2—S1—O4s	104.8 (9)	100.8 (9)	106.3 (9)
O2s—S1—O3s	110.62 (8)	110.08 (8)	111.03 (8)
O2s—S1—O4s	111.3 (9)	109.7 (9)	112.0 (9)
O3s—S1—O4s	110.4 (10)	106.2 (10)	112.2 (10)
Fe1—O1b1—S1	150.3 (4)	145.7 (6)	152.5 (3)
Fe1—O1b2—S1	148.9 (4)	143.7 (5)	150.8 (2)
Fe1—O5w1—H1o5w1	120.0 (15)	117.9 (14)	120.9 (16)
Fe1—O5w1—H2o5w1	128.4 (15)	127.6 (16)	130.1 (13)
H1o5w1—O5w1—H2o5w1	111 (2)	111 (2)	111 (2)
Fe1—O5w2—H1o5w2	113.9 (14)	113.0 (13)	114.2 (15)
Fe1—O5w2—H2o5w2	125.6 (16)	124.3 (14)	126.2 (18)
H1o5w2—O5w2—H2o5w2	108.4 (19)	108.4 (19)	108.4 (19)
Fe1—O6w—H1o6w	115.5 (12)	113.0 (12)	118.3 (12)
Fe1—O6w—H2o6w	127.1 (10)	121.9 (9)	131.5 (10)
H1o6w—O6w—H2o6w	114.4 (15)	114.4 (16)	114.4 (16)
C1—N1—H1n1	119.0 (17)	118.7 (17)	119.3 (17)
C1—N1—H1n1^ii	119.0 (17)	118.7 (17)	119.3 (17)
C1—N1—H2n1	118.1 (17)	117.3 (17)	118.9 (17)
C1—N1—H2n1^ii	118.1 (17)	117.3 (17)	118.9 (17)
H1n1—N1—H1n1^ii	122 (2)	122 (2)	122 (2)
H1n1—N1—H2n1	107 (2)	107 (2)	108 (2)
H1n1—N1—H2n1^ii	41 (2)	40 (2)	41 (2)
H1n1^ii—N1—H2n1	41 (2)	40 (2)	41 (2)
H1n1^ii—N1—H2n1^ii	107 (2)	107 (2)	108 (2)
H2n1—N1—H2n1^ii	124 (2)	123 (2)	125 (2)
C3—N2—C3^ii	121.31 (17)	121.2 (2)	121.4 (2)
C3—N2—H1n2	119.34	119.31	119.38
C3^ii—N2—H1n2	119.34	119.31	119.38
N1—C1—C2	121.39 (13)	120.66 (16)	122.13 (16)
N1—C1—C2^ii	121.39 (13)	120.66 (16)	122.13 (16)
C2—C1—C2^ii	117.22 (18)	117.1 (2)	117.3 (2)
C1—C2—C3	120.12 (17)	120.03 (17)	120.22 (17)
C1—C2—H1c2	119.94	119.89	119.98
C3—C2—H1c2	119.94	119.89	119.99
N2—C3—C2	120.60 (18)	120.56 (17)	120.65 (17)
N2—C3—H1c3	119.7	119.68	119.72
C2—C3—H1c3	119.7	119.67	119.72
N1—H1n1—H2n1^ii	70 (3)	69 (3)	70 (3)
N1—H2n1—H1n1^ii	70 (3)	69 (3)	70 (3)

Symmetry codes: (i) −x₁+2, x₂, −x₃+1/2, −x₄+1/2; (ii) −x₁+1, x₂, −x₃+1/2, −x₄+1/2.

(PhaseIV)

Crystal data

C5H15FeN2O12S2	Z = 4
Mr = 415.16	F(000) = 852
Triclinic, P1	Dx = 1.997 Mg m^−3
a = 10.516 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.873 (4) Å	Cell parameters from 2322 reflections
c = 13.099 (4) Å	θ = 2.4–29.3°
α = 65.34 (3)°	µ = 1.46 mm^−1
β = 77.51 (3)°	T = 80 K
γ = 68.73 (3)°	Block, yellow
V = 1381.0 (9) Å^3	0.47 × 0.40 × 0.27 mm

Data collection

Xcalibur, Atlas diffractometer	5963 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.018
ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: analytical CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→12
Tmin = 0.592, Tmax = 0.764	k = −14→14
7895 measured reflections	l = −16→16
7895 independent reflections

Refinement

Refinement on F^2	28 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0453P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
7895 reflections	Δρmax = 0.36 e Å^−3
446 parameters	Δρmin = −0.60 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. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq
Fe1	0.85489 (5)	0.80465 (5)	0.05110 (4)	0.00606 (9)
O11W	0.8995 (2)	0.7303 (2)	−0.06833 (19)	0.0149 (5)
H11A	0.895 (3)	0.659 (2)	−0.062 (2)	0.022*
H11B	0.917 (3)	0.785 (2)	−0.1299 (18)	0.022*
O12W	1.0244 (2)	0.8607 (2)	−0.00306 (17)	0.0180 (5)
H12A	1.090 (2)	0.848 (2)	0.032 (2)	0.027*
H12B	1.035 (3)	0.899 (2)	−0.0698 (16)	0.027*
O13W	0.81186 (18)	0.87453 (18)	0.17633 (15)	0.0121 (4)
H13A	0.797 (2)	0.821 (2)	0.2440 (16)	0.018*
H13B	0.855 (3)	0.909 (2)	0.196 (2)	0.018*
O14W	0.6785 (2)	0.7595 (2)	0.10258 (19)	0.0129 (5)
H14A	0.600 (2)	0.812 (2)	0.078 (2)	0.019*
H14B	0.659 (3)	0.716 (2)	0.1693 (16)	0.019*
S11	1.02552 (8)	0.49807 (7)	0.19250 (6)	0.00594 (17)
O11	0.94714 (15)	0.63949 (14)	0.16268 (12)	0.0119 (3)
O12	1.1177 (2)	0.4786 (2)	0.09617 (18)	0.0117 (5)
O13	1.1034 (2)	0.4622 (2)	0.28774 (19)	0.0105 (5)
O14	0.9275 (2)	0.4234 (2)	0.2238 (2)	0.0120 (5)
S12	0.67609 (8)	1.10656 (8)	−0.09414 (6)	0.00639 (18)
O15	0.75980 (15)	0.96622 (14)	−0.06330 (12)	0.0140 (3)
O16	0.7677 (2)	1.1834 (2)	−0.10813 (19)	0.0129 (5)
O17	0.6192 (2)	1.14596 (19)	−0.19994 (18)	0.0115 (5)
O18	0.5663 (2)	1.1188 (2)	−0.00516 (19)	0.0106 (5)
Fe2	0.14147 (5)	0.69703 (5)	0.44620 (4)	0.00613 (9)
O21W	0.12655 (18)	0.67397 (18)	0.30560 (15)	0.0138 (4)
H21A	0.160 (2)	0.717 (2)	0.2402 (16)	0.021*
H21B	0.126 (3)	0.607 (2)	0.299 (2)	0.021*
O22W	0.3376 (2)	0.69092 (19)	0.39982 (19)	0.0136 (5)
H22A	0.406 (2)	0.656 (2)	0.433 (2)	0.020*
H22B	0.359 (3)	0.750 (2)	0.3361 (18)	0.020*
O23W	0.1403 (2)	0.73612 (19)	0.58166 (18)	0.0106 (5)
H23A	0.129 (3)	0.8129 (19)	0.576 (2)	0.016*
H23B	0.106 (3)	0.690 (2)	0.6342 (18)	0.016*
O24W	−0.05504 (19)	0.69447 (17)	0.49652 (16)	0.0105 (4)
H24A	−0.062 (3)	0.645 (2)	0.5571 (17)	0.016*
H24B	−0.108 (2)	0.697 (2)	0.4532 (19)	0.016*
S21	0.30787 (8)	0.39157 (8)	0.58710 (7)	0.00705 (17)
O21	0.19184 (14)	0.51098 (14)	0.53521 (12)	0.0121 (3)
O22	0.4257 (2)	0.3861 (2)	0.50322 (18)	0.0105 (5)
O23	0.34297 (19)	0.39600 (19)	0.68592 (18)	0.0114 (5)
O24	0.2543 (2)	0.2805 (2)	0.61826 (19)	0.0101 (5)
S22	−0.01189 (8)	1.01117 (7)	0.31362 (6)	0.00706 (19)
O25	0.09707 (15)	0.88340 (14)	0.35703 (13)	0.0125 (3)
O26	0.0580 (2)	1.11249 (19)	0.27131 (19)	0.0102 (5)
O27	−0.0733 (2)	1.0135 (2)	0.22243 (18)	0.0126 (5)
O28	−0.1149 (2)	1.0298 (2)	0.40460 (19)	0.0125 (6)
N11	0.6558 (3)	0.4454 (3)	0.1977 (3)	0.0104 (4)
H11	0.7086	0.4706	0.2218	0.013*
C12	0.7124 (4)	0.3670 (4)	0.1404 (3)	0.0134 (9)
H12	0.8092	0.3391	0.1273	0.016*
C13	0.6372 (4)	0.3262 (4)	0.1007 (3)	0.0114 (8)
H13	0.6801	0.2693	0.0609	0.014*
C14	0.4888 (5)	0.3704 (5)	0.1195 (4)	0.0103 (4)
N14	0.4103 (3)	0.3316 (3)	0.0820 (3)	0.0122 (4)
H14C	0.3208	0.3574	0.0954	0.015*
H14D	0.4480	0.2800	0.0439	0.015*
C15	0.4343 (4)	0.4506 (4)	0.1793 (3)	0.0124 (9)
H15	0.3378	0.4813	0.1930	0.015*
C16	0.5167 (4)	0.4877 (4)	0.2198 (3)	0.0127 (8)
H16	0.4778	0.5418	0.2624	0.015*
N21	0.3527 (3)	0.0502 (3)	0.2988 (3)	0.0124 (4)
H21	0.3015	0.0243	0.2737	0.015*
C22	0.4918 (4)	0.0105 (4)	0.2774 (3)	0.0126 (9)
H22	0.5327	−0.0428	0.2342	0.015*
C23	0.5721 (4)	0.0488 (4)	0.3193 (3)	0.0119 (9)
H23	0.6688	0.0197	0.3060	0.014*
C24	0.5145 (4)	0.1282 (5)	0.3797 (4)	0.0097 (4)
N24	0.5907 (3)	0.1685 (3)	0.4186 (3)	0.0128 (4)
H24C	0.6803	0.1441	0.4055	0.015*
H24D	0.5513	0.2194	0.4571	0.015*
C25	0.3660 (4)	0.1699 (4)	0.3980 (3)	0.0131 (9)
H25	0.3211	0.2261	0.4382	0.016*
C26	0.2936 (4)	0.1276 (4)	0.3572 (3)	0.0142 (9)
H26	0.1968	0.1536	0.3702	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0051 (3)	0.0058 (2)	0.0068 (3)	−0.00186 (18)	−0.00046 (19)	−0.00176 (16)
O11W	0.0279 (12)	0.0102 (11)	0.0083 (9)	−0.0088 (9)	0.0026 (8)	−0.0045 (8)
O12W	0.0152 (10)	0.0302 (13)	0.0087 (9)	−0.0165 (9)	−0.0027 (8)	0.0016 (9)
O13W	0.0186 (10)	0.0124 (10)	0.0086 (9)	−0.0088 (8)	0.0010 (8)	−0.0046 (8)
O14W	0.0106 (9)	0.0195 (12)	0.0090 (9)	−0.0082 (9)	−0.0008 (7)	−0.0025 (9)
S11	0.0060 (3)	0.0058 (4)	0.0063 (3)	−0.0023 (3)	−0.0004 (3)	−0.0021 (3)
O11	0.0138 (8)	0.0065 (8)	0.0111 (8)	0.0009 (7)	−0.0020 (6)	−0.0022 (6)
O12	0.0113 (12)	0.0139 (13)	0.0082 (11)	−0.0022 (10)	0.0018 (9)	−0.0051 (9)
O13	0.0099 (10)	0.0111 (10)	0.0116 (9)	−0.0034 (8)	−0.0009 (7)	−0.0050 (7)
O14	0.0089 (9)	0.0158 (11)	0.0122 (9)	−0.0061 (8)	−0.0021 (7)	−0.0034 (8)
S12	0.0060 (3)	0.0064 (4)	0.0065 (3)	−0.0013 (3)	−0.0009 (3)	−0.0024 (3)
O15	0.0139 (8)	0.0106 (9)	0.0131 (8)	0.0007 (7)	−0.0020 (6)	−0.0035 (7)
O16	0.0130 (10)	0.0173 (12)	0.0103 (10)	−0.0083 (9)	−0.0020 (8)	−0.0033 (9)
O17	0.0149 (10)	0.0099 (11)	0.0090 (9)	−0.0055 (8)	−0.0015 (7)	−0.0011 (8)
O18	0.0083 (12)	0.0158 (13)	0.0115 (11)	−0.0041 (10)	0.0015 (9)	−0.0093 (10)
Fe2	0.0050 (3)	0.0061 (2)	0.0068 (3)	−0.00194 (18)	−0.00057 (19)	−0.00165 (16)
O21W	0.0234 (11)	0.0149 (11)	0.0083 (9)	−0.0122 (9)	−0.0003 (8)	−0.0043 (8)
O22W	0.0071 (9)	0.0140 (12)	0.0114 (10)	−0.0015 (9)	−0.0025 (7)	0.0024 (9)
O23W	0.0172 (11)	0.0073 (11)	0.0079 (9)	−0.0056 (8)	0.0011 (8)	−0.0026 (8)
O24W	0.0090 (9)	0.0132 (10)	0.0092 (9)	−0.0056 (8)	−0.0016 (7)	−0.0018 (8)
S21	0.0063 (3)	0.0061 (4)	0.0079 (3)	−0.0013 (3)	0.0002 (3)	−0.0027 (3)
O21	0.0097 (8)	0.0109 (8)	0.0142 (8)	−0.0036 (7)	−0.0013 (6)	−0.0029 (6)
O22	0.0089 (12)	0.0144 (13)	0.0100 (11)	−0.0035 (10)	0.0007 (9)	−0.0069 (9)
O23	0.0112 (10)	0.0145 (12)	0.0092 (9)	−0.0054 (8)	−0.0023 (8)	−0.0031 (8)
O24	0.0137 (10)	0.0080 (11)	0.0092 (9)	−0.0054 (8)	−0.0019 (7)	−0.0016 (8)
S22	0.0074 (3)	0.0061 (4)	0.0064 (3)	−0.0019 (3)	−0.0002 (3)	−0.0013 (3)
O25	0.0109 (8)	0.0082 (8)	0.0138 (8)	0.0000 (7)	−0.0011 (6)	−0.0021 (7)
O26	0.0150 (10)	0.0089 (11)	0.0109 (9)	−0.0077 (8)	−0.0014 (7)	−0.0041 (8)
O27	0.0159 (11)	0.0164 (11)	0.0092 (10)	−0.0093 (9)	−0.0031 (8)	−0.0034 (8)
O28	0.0110 (13)	0.0125 (12)	0.0097 (11)	−0.0006 (10)	0.0011 (9)	−0.0036 (9)
N11	0.0072 (12)	0.0110 (11)	0.0127 (11)	−0.0029 (9)	−0.0049 (9)	−0.0020 (8)
C12	0.0095 (18)	0.014 (2)	0.016 (2)	−0.0037 (15)	−0.0030 (15)	−0.0040 (16)
C13	0.0061 (18)	0.0085 (19)	0.0155 (19)	0.0012 (15)	0.0007 (15)	−0.0043 (16)
C14	0.007 (2)	0.0102 (15)	0.0089 (16)	−0.0030 (11)	−0.0019 (12)	0.0020 (10)
N14	0.0075 (17)	0.0146 (13)	0.0202 (15)	−0.0051 (10)	0.0026 (11)	−0.0120 (9)
C15	0.0080 (18)	0.016 (2)	0.0160 (19)	−0.0055 (16)	−0.0004 (15)	−0.0067 (17)
C16	0.0101 (18)	0.011 (2)	0.0132 (19)	−0.0013 (14)	−0.0009 (14)	−0.0028 (16)
N21	0.0093 (13)	0.0135 (11)	0.0148 (11)	−0.0047 (9)	−0.0046 (9)	−0.0029 (8)
C22	0.0099 (18)	0.013 (2)	0.0130 (19)	−0.0015 (15)	0.0014 (14)	−0.0053 (16)
C23	0.0072 (17)	0.015 (2)	0.0160 (19)	−0.0062 (15)	0.0009 (15)	−0.0064 (17)
C24	0.0048 (19)	0.0103 (16)	0.0084 (16)	−0.0019 (11)	−0.0017 (11)	0.0019 (10)
N24	0.0084 (17)	0.0144 (13)	0.0210 (15)	−0.0053 (10)	0.0022 (11)	−0.0117 (9)
C25	0.0065 (18)	0.013 (2)	0.018 (2)	0.0000 (15)	0.0014 (16)	−0.0079 (17)
C26	0.0088 (18)	0.019 (2)	0.016 (2)	−0.0043 (16)	−0.0002 (15)	−0.0079 (17)

Geometric parameters (Å, º)

Fe1—O11	1.9401 (18)	S21—O23	1.446 (2)
Fe1—O15	1.9451 (18)	S21—O22	1.470 (2)
Fe1—O11W	1.995 (2)	S21—O24	1.488 (2)
Fe1—O12W	2.011 (2)	S21—O21	1.5034 (18)
Fe1—O14W	2.015 (2)	S22—O28	1.460 (2)
Fe1—O13W	2.031 (2)	S22—O27	1.462 (3)
O11W—H11A	0.828 (18)	S22—O26	1.484 (2)
O11W—H11B	0.832 (18)	S22—O25	1.4961 (18)
O12W—H12A	0.852 (19)	N11—C12	1.330 (5)
O12W—H12B	0.804 (18)	N11—C16	1.371 (5)
O13W—H13A	0.868 (18)	N11—H11	0.8800
O13W—H13B	0.836 (19)	C12—C13	1.341 (5)
O14W—H14A	0.867 (19)	C12—H12	0.9500
O14W—H14B	0.835 (18)	C13—C14	1.456 (6)
S11—O12	1.462 (2)	C13—H13	0.9500
S11—O13	1.467 (3)	C14—N14	1.332 (2)
S11—O14	1.481 (2)	C14—C15	1.372 (6)
S11—O11	1.4964 (18)	N14—H14C	0.8800
S12—O17	1.453 (2)	N14—H14D	0.8800
S12—O18	1.466 (2)	C15—C16	1.377 (5)
S12—O16	1.488 (3)	C15—H15	0.9500
S12—O15	1.4975 (18)	C16—H16	0.9500
Fe2—O21	1.9465 (18)	N21—C26	1.335 (5)
Fe2—O25	1.9514 (18)	N21—C22	1.368 (5)
Fe2—O22W	2.003 (2)	N21—H21	0.8800
Fe2—O23W	2.009 (2)	C22—C23	1.381 (5)
Fe2—O21W	2.0171 (19)	C22—H22	0.9500
Fe2—O24W	2.036 (2)	C23—C24	1.372 (6)
O21W—H21A	0.867 (18)	C23—H23	0.9500
O21W—H21B	0.838 (19)	C24—N24	1.337 (2)
O22W—H22A	0.808 (18)	C24—C25	1.456 (6)
O22W—H22B	0.887 (18)	N24—H24C	0.8800
O23W—H23A	0.846 (18)	N24—H24D	0.8800
O23W—H23B	0.786 (18)	C25—C26	1.340 (6)
O24W—H24A	0.773 (18)	C25—H25	0.9500
O24W—H24B	0.863 (18)	C26—H26	0.9500
O11—Fe1—O15	177.57 (7)	Fe2—O23W—H23A	120.9 (19)
O11—Fe1—O11W	92.71 (8)	Fe2—O23W—H23B	109 (2)
O15—Fe1—O11W	85.35 (9)	H23A—O23W—H23B	120 (3)
O11—Fe1—O12W	93.61 (8)	Fe2—O24W—H24A	113 (2)
O15—Fe1—O12W	87.83 (8)	Fe2—O24W—H24B	122.9 (17)
O11W—Fe1—O12W	89.22 (9)	H24A—O24W—H24B	112 (3)
O11—Fe1—O14W	89.35 (9)	O23—S21—O22	110.76 (15)
O15—Fe1—O14W	89.26 (9)	O23—S21—O24	110.81 (13)
O11W—Fe1—O14W	92.19 (7)	O22—S21—O24	111.56 (15)
O12W—Fe1—O14W	176.66 (9)	O23—S21—O21	109.73 (11)
O11—Fe1—O13W	85.48 (8)	O22—S21—O21	108.90 (11)
O15—Fe1—O13W	96.45 (8)	O24—S21—O21	104.89 (12)
O11W—Fe1—O13W	178.18 (8)	S21—O21—Fe2	144.75 (10)
O12W—Fe1—O13W	91.11 (7)	O28—S22—O27	110.94 (16)
O14W—Fe1—O13W	87.57 (8)	O28—S22—O26	109.94 (15)
Fe1—O11W—H11A	127 (2)	O27—S22—O26	110.83 (13)
Fe1—O11W—H11B	109 (2)	O28—S22—O25	110.10 (12)
H11A—O11W—H11B	123 (3)	O27—S22—O25	108.87 (12)
Fe1—O12W—H12A	131.0 (19)	O26—S22—O25	106.04 (12)
Fe1—O12W—H12B	116 (2)	S22—O25—Fe2	147.48 (10)
H12A—O12W—H12B	113 (3)	C12—N11—C16	121.33 (17)
Fe1—O13W—H13A	116.6 (17)	C12—N11—H11	119.3
Fe1—O13W—H13B	131 (2)	C16—N11—H11	119.3
H13A—O13W—H13B	95 (3)	N11—C12—C13	122.1 (4)
Fe1—O14W—H14A	124.4 (18)	N11—C12—H12	119.0
Fe1—O14W—H14B	123 (2)	C13—C12—H12	119.0
H14A—O14W—H14B	104 (3)	C12—C13—C14	119.0 (4)
O12—S11—O13	110.68 (16)	C12—C13—H13	120.5
O12—S11—O14	110.09 (16)	C14—C13—H13	120.5
O13—S11—O14	111.55 (13)	N14—C14—C15	121.9 (5)
O12—S11—O11	109.71 (11)	N14—C14—C13	120.9 (5)
O13—S11—O11	105.85 (12)	C15—C14—C13	117.21 (18)
O14—S11—O11	108.85 (12)	C14—N14—H14C	120.0
S11—O11—Fe1	148.86 (10)	C14—N14—H14D	120.0
O17—S12—O18	110.48 (14)	H14C—N14—H14D	120.0
O17—S12—O16	110.52 (12)	C14—C15—C16	121.3 (4)
O18—S12—O16	111.59 (16)	C14—C15—H15	119.3
O17—S12—O15	106.79 (12)	C16—C15—H15	119.3
O18—S12—O15	108.82 (12)	N11—C16—C15	119.1 (4)
O16—S12—O15	108.50 (12)	N11—C16—H16	120.5
S12—O15—Fe1	148.09 (10)	C15—C16—H16	120.5
O21—Fe2—O25	178.14 (7)	C26—N21—C22	120.97 (17)
O21—Fe2—O22W	92.16 (8)	C26—N21—H21	119.5
O25—Fe2—O22W	86.06 (8)	C22—N21—H21	119.5
O21—Fe2—O23W	91.07 (8)	N21—C22—C23	119.4 (4)
O25—Fe2—O23W	88.43 (8)	N21—C22—H22	120.3
O22W—Fe2—O23W	92.40 (7)	C23—C22—H22	120.3
O21—Fe2—O21W	93.49 (8)	C24—C23—C22	121.1 (4)
O25—Fe2—O21W	87.12 (8)	C24—C23—H23	119.5
O22W—Fe2—O21W	90.87 (8)	C22—C23—H23	119.5
O23W—Fe2—O21W	174.29 (8)	N24—C24—C23	121.7 (5)
O21—Fe2—O24W	85.32 (8)	N24—C24—C25	120.8 (5)
O25—Fe2—O24W	96.46 (8)	C23—C24—C25	117.40 (18)
O22W—Fe2—O24W	177.46 (8)	C24—N24—H24C	120.0
O23W—Fe2—O24W	87.98 (8)	C24—N24—H24D	120.0
O21W—Fe2—O24W	88.96 (7)	H24C—N24—H24D	120.0
Fe2—O21W—H21A	121.4 (17)	C26—C25—C24	118.8 (4)
Fe2—O21W—H21B	129 (2)	C26—C25—H25	120.6
H21A—O21W—H21B	104 (3)	C24—C25—H25	120.6
Fe2—O22W—H22A	133.4 (19)	N21—C26—C25	122.4 (4)
Fe2—O22W—H22B	120.1 (18)	N21—C26—H26	118.8
H22A—O22W—H22B	104 (3)	C25—C26—H26	118.8
O12—S11—O11—Fe1	36.7 (3)	C12—C13—C14—N14	−179.6 (4)
O13—S11—O11—Fe1	156.16 (19)	C12—C13—C14—C15	−1.1 (8)
O14—S11—O11—Fe1	−83.8 (2)	N14—C14—C15—C16	178.5 (4)
O17—S12—O15—Fe1	−165.54 (18)	C13—C14—C15—C16	0.0 (8)
O18—S12—O15—Fe1	−46.3 (2)	C12—N11—C16—C15	−1.6 (7)
O16—S12—O15—Fe1	75.3 (2)	C14—C15—C16—N11	1.4 (7)
O23—S21—O21—Fe2	74.87 (19)	C26—N21—C22—C23	1.5 (7)
O22—S21—O21—Fe2	−46.5 (2)	N21—C22—C23—C24	−1.4 (7)
O24—S21—O21—Fe2	−166.06 (17)	C22—C23—C24—N24	−178.4 (4)
O28—S22—O25—Fe2	46.8 (2)	C22—C23—C24—C25	0.1 (8)
O27—S22—O25—Fe2	−75.0 (2)	N24—C24—C25—C26	179.7 (4)
O26—S22—O25—Fe2	165.68 (18)	C23—C24—C25—C26	1.1 (8)
C16—N11—C12—C13	0.5 (8)	C22—N21—C26—C25	−0.3 (8)
N11—C12—C13—C14	0.8 (7)	C24—C25—C26—N21	−1.1 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O12^i	0.83 (2)	1.93 (2)	2.726 (4)	162 (3)
O11W—H11B···O26^ii	0.83 (2)	1.77 (2)	2.589 (3)	169 (3)
O12W—H12A···O16^iii	0.85 (2)	1.81 (2)	2.662 (3)	178 (3)
O12W—H12B···O27^ii	0.80 (2)	1.86 (2)	2.662 (3)	175 (3)
O13W—H13A···O24^iv	0.87 (2)	1.80 (2)	2.664 (3)	173 (2)
O13W—H13B···O27^v	0.84 (2)	1.85 (2)	2.672 (3)	169 (3)
O14W—H14A···O18^ii	0.87 (2)	1.91 (2)	2.743 (3)	160 (3)
O14W—H14B···O23^iv	0.84 (2)	1.81 (2)	2.627 (3)	168 (3)
O21W—H21A···O16^ii	0.867 (18)	1.830 (18)	2.695 (3)	175 (3)
O21W—H21B···O13^vi	0.838 (19)	1.885 (19)	2.720 (3)	174 (3)
O22W—H22A···O22^iv	0.808 (18)	1.93 (2)	2.719 (4)	166 (3)
O22W—H22B···O17^ii	0.887 (18)	1.716 (19)	2.589 (3)	167 (3)
O23W—H23A···O28^vii	0.846 (18)	1.941 (19)	2.773 (3)	167 (3)
O23W—H23B···O14^iv	0.786 (18)	1.838 (19)	2.599 (3)	163 (3)
O24W—H24A···O13^iv	0.773 (18)	1.948 (19)	2.717 (3)	172 (3)
O24W—H24B···O24^viii	0.863 (18)	1.850 (19)	2.698 (3)	167 (2)
N11—H11···O14	0.88	2.17	2.856 (3)	135
N11—H11···O23^iv	0.88	2.23	2.880 (3)	131
N14—H14C···O12^vi	0.88	2.10	2.945 (5)	161
N14—H14D···O18^ix	0.88	2.14	2.994 (4)	164
C15—H15···O13^vi	0.95	2.55	3.439 (5)	155
C16—H16···O23^iv	0.95	2.56	3.050 (5)	113
N21—H21···O17^x	0.88	2.40	3.006 (4)	126
N21—H21···O26^ix	0.88	2.39	2.980 (4)	125
C22—H22···O17^x	0.95	2.54	3.083 (5)	117
N24—H24C···O28^xi	0.88	2.09	2.938 (5)	162
N24—H24D···O22	0.88	2.19	3.036 (4)	162
C25—H25···O24	0.95	2.59	3.464 (5)	154
C26—H26···O26^ix	0.95	2.43	3.022 (5)	120

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+2, −z; (iii) −x+2, −y+2, −z; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z; (vi) x−1, y, z; (vii) −x, −y+2, −z+1; (viii) −x, −y+1, −z+1; (ix) x, y−1, z; (x) −x+1, −y+1, −z; (xi) x+1, y−1, z.