Isotypic Mn^II and Fe^II binuclear complexes of the ligand 5,6-bis­(pyridin-2-yl)-pyrazine-2,3-di­carb­oxy­lic acid

The reaction of manganese dichloride and iron dichloride with the ligand 5,6-bis­(pyridin-2-yl)pyrazine-2,3-di­carb­oxy­lic acid leads to the formation of isotypic binuclear complexes which have a cage-like structure.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.045
• wR factor = 0.108
• Data-to-parameter ratio = 11.0

Structure: II

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.116
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT018_ALERT_1_C _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         12 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          8 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          8 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) Still          71 %
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           2 Note

   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
   9 ALERT level G = General information/check it is not something unexpected

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




Datablock: II


Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full value Low .      0.940 Note
PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L=  0.600        194 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         12 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          8 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          8 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         34 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           2 Note

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

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

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Computing details

Data collection: STADI4 Software (Stoe & Cie, 1997) for (I); EXPOSE in IPDS-I (Stoe & Cie, 2004) for (II). Cell refinement: STADI4 Software (Stoe & Cie, 1997) for (I); CELL in IPDS-I (Stoe & Cie, 2004) for (II). Data reduction: X-RED Software (Stoe & Cie, 1997) for (I); INTEGRATE in IPDS-I (Stoe & Cie, 2004) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(I) Bis[µ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ⁴N¹,O²,N⁶:O³;κ⁴O³:N¹,O²,N⁶-bis[diaquamanganese(II)] tetrahydrate

Crystal data

[Mn2(C16H8N4O4)2(H2O)4]·4H2O	Z = 1
Mr = 894.53	F(000) = 458
Triclinic, P1	Dx = 1.610 Mg m^−3
a = 8.148 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4408 (13) Å	Cell parameters from 22 reflections
c = 11.5796 (11) Å	θ = 14.0–19.7°
α = 70.527 (8)°	µ = 0.77 mm^−1
β = 84.232 (9)°	T = 293 K
γ = 84.849 (8)°	Block, yellow
V = 922.4 (8) Å^3	0.38 × 0.27 × 0.23 mm

Data collection

Stoe-Siemens AED2, 4-circle diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.1°
Plane graphite monochromator	h = −9→9
ω/\2q scans	k = −11→12
3244 measured reflections	l = 0→13
3244 independent reflections	3 standard reflections every 60 min
2689 reflections with I > 2σ(I)	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: mixed
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 1.0007P] where P = (Fo^2 + 2Fc^2)/3
3244 reflections	(Δ/σ)max < 0.001
294 parameters	Δρmax = 0.45 e Å^−3
8 restraints	Δρmin = −0.40 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.

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

	x	y	z	Uiso*/Ueq
Mn1	0.70864 (6)	0.99063 (5)	0.82620 (4)	0.02391 (16)
N1	0.9248 (3)	0.8600 (3)	0.9156 (2)	0.0206 (6)
N2	1.1681 (3)	0.6867 (3)	1.0396 (2)	0.0235 (6)
N3	0.8377 (4)	0.8748 (3)	0.7001 (3)	0.0312 (7)
N4	1.4257 (3)	0.6290 (3)	0.8621 (3)	0.0321 (7)
O1	0.7117 (3)	1.0051 (2)	1.0136 (2)	0.0265 (5)
O2	0.8025 (3)	0.9040 (3)	1.2007 (2)	0.0319 (6)
O3	1.1805 (3)	0.8180 (2)	1.2502 (2)	0.0304 (5)
O4	1.0455 (3)	0.6281 (3)	1.3049 (2)	0.0365 (6)
O1W	0.5391 (3)	0.8379 (3)	0.9213 (3)	0.0357 (6)
H1WA	0.455 (4)	0.875 (4)	0.946 (4)	0.051 (13)*
H1WB	0.505 (5)	0.774 (3)	0.903 (4)	0.053 (14)*
O2W	0.5185 (3)	1.0850 (3)	0.7038 (3)	0.0424 (7)
H2WA	0.419 (3)	1.079 (5)	0.733 (4)	0.058 (15)*
H2WB	0.523 (5)	1.166 (2)	0.659 (4)	0.052 (14)*
C1	0.9384 (4)	0.8447 (3)	1.0332 (3)	0.0199 (6)
C2	1.0656 (4)	0.7588 (3)	1.0956 (3)	0.0209 (7)
C3	1.1502 (4)	0.6992 (3)	0.9223 (3)	0.0215 (7)
C4	1.0271 (4)	0.7907 (3)	0.8571 (3)	0.0221 (7)
C5	0.9896 (4)	0.8167 (3)	0.7265 (3)	0.0251 (7)
C6	1.0980 (5)	0.7841 (4)	0.6389 (3)	0.0352 (9)
H6	1.2053	0.7500	0.6567	0.042*
C7	1.0440 (6)	0.8031 (4)	0.5245 (3)	0.0446 (10)
H7	1.1148	0.7812	0.4647	0.053*
C8	0.8856 (6)	0.8542 (4)	0.4996 (3)	0.0466 (11)
H8	0.8455	0.8634	0.4247	0.056*
C9	0.7872 (5)	0.8917 (4)	0.5885 (3)	0.0423 (10)
H9	0.6815	0.9303	0.5706	0.051*
C10	1.2647 (4)	0.6068 (3)	0.8723 (3)	0.0220 (7)
C11	1.2058 (4)	0.5036 (3)	0.8415 (3)	0.0315 (8)
H11	1.0930	0.4917	0.8485	0.038*
C12	1.3179 (5)	0.4179 (4)	0.7999 (3)	0.0359 (9)
H12	1.2817	0.3471	0.7790	0.043*
C13	1.4837 (5)	0.4392 (4)	0.7900 (3)	0.0382 (9)
H13	1.5615	0.3834	0.7621	0.046*
C14	1.5315 (5)	0.5442 (4)	0.8220 (4)	0.0398 (9)
H14	1.6438	0.5576	0.8156	0.048*
C15	0.8067 (4)	0.9252 (3)	1.0883 (3)	0.0220 (7)
C16	1.0965 (4)	0.7345 (3)	1.2291 (3)	0.0249 (7)
O3W	0.5321 (5)	0.3184 (4)	0.5099 (3)	0.0592 (9)
H3WA	0.441 (4)	0.361 (4)	0.496 (4)	0.063 (16)*
H3WB	0.605 (5)	0.376 (4)	0.496 (5)	0.064 (17)*
O4W	0.2287 (4)	0.4854 (4)	0.5048 (3)	0.0541 (8)
H4WA	0.156 (5)	0.450 (5)	0.561 (4)	0.09 (2)*
H4WB	0.177 (6)	0.528 (5)	0.443 (4)	0.09 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0229 (3)	0.0281 (3)	0.0212 (3)	0.0047 (2)	−0.00536 (19)	−0.0092 (2)
N1	0.0206 (13)	0.0254 (14)	0.0170 (13)	0.0020 (11)	−0.0013 (10)	−0.0094 (11)
N2	0.0227 (14)	0.0255 (14)	0.0241 (14)	0.0032 (11)	−0.0052 (11)	−0.0108 (12)
N3	0.0327 (16)	0.0421 (18)	0.0229 (15)	0.0071 (13)	−0.0094 (12)	−0.0164 (13)
N4	0.0252 (15)	0.0384 (17)	0.0387 (17)	0.0029 (13)	−0.0029 (13)	−0.0216 (14)
O1	0.0291 (12)	0.0296 (12)	0.0214 (12)	0.0084 (10)	−0.0043 (10)	−0.0110 (10)
O2	0.0309 (13)	0.0458 (15)	0.0210 (12)	0.0088 (11)	−0.0020 (10)	−0.0164 (11)
O3	0.0360 (14)	0.0363 (14)	0.0222 (12)	−0.0046 (11)	−0.0076 (10)	−0.0117 (10)
O4	0.0466 (16)	0.0360 (15)	0.0234 (13)	−0.0105 (12)	−0.0068 (11)	−0.0020 (11)
O1W	0.0290 (14)	0.0340 (15)	0.0490 (17)	−0.0058 (12)	0.0061 (12)	−0.0218 (13)
O2W	0.0254 (15)	0.0521 (19)	0.0360 (16)	0.0046 (13)	−0.0067 (12)	0.0031 (14)
C1	0.0225 (16)	0.0194 (16)	0.0172 (15)	−0.0022 (13)	0.0000 (12)	−0.0054 (12)
C2	0.0200 (16)	0.0236 (16)	0.0206 (16)	−0.0034 (13)	−0.0028 (13)	−0.0083 (13)
C3	0.0216 (16)	0.0218 (16)	0.0220 (16)	−0.0013 (13)	−0.0027 (13)	−0.0082 (13)
C4	0.0243 (17)	0.0245 (17)	0.0190 (16)	0.0026 (13)	−0.0032 (13)	−0.0096 (13)
C5	0.0330 (19)	0.0270 (17)	0.0169 (16)	0.0049 (14)	−0.0045 (14)	−0.0101 (14)
C6	0.040 (2)	0.041 (2)	0.0242 (18)	0.0142 (17)	−0.0039 (15)	−0.0133 (16)
C7	0.071 (3)	0.044 (2)	0.0187 (18)	0.012 (2)	0.0017 (18)	−0.0150 (17)
C8	0.071 (3)	0.051 (3)	0.0219 (19)	0.011 (2)	−0.0142 (19)	−0.0184 (18)
C9	0.046 (2)	0.054 (3)	0.031 (2)	0.0112 (19)	−0.0190 (18)	−0.0183 (19)
C10	0.0229 (16)	0.0230 (16)	0.0201 (16)	0.0048 (13)	−0.0050 (13)	−0.0078 (13)
C11	0.0291 (18)	0.0278 (19)	0.038 (2)	−0.0011 (15)	−0.0004 (15)	−0.0122 (16)
C12	0.049 (2)	0.0256 (19)	0.036 (2)	0.0006 (17)	−0.0038 (17)	−0.0142 (16)
C13	0.041 (2)	0.039 (2)	0.038 (2)	0.0157 (17)	−0.0044 (17)	−0.0209 (18)
C14	0.0249 (19)	0.051 (2)	0.051 (2)	0.0086 (17)	−0.0060 (17)	−0.029 (2)
C15	0.0206 (16)	0.0254 (17)	0.0229 (17)	−0.0040 (13)	−0.0004 (13)	−0.0113 (14)
C16	0.0221 (17)	0.0307 (19)	0.0223 (17)	0.0063 (14)	−0.0058 (13)	−0.0100 (15)
O3W	0.052 (2)	0.050 (2)	0.062 (2)	0.0047 (18)	−0.0119 (17)	0.0001 (16)
O4W	0.0378 (17)	0.066 (2)	0.0458 (19)	0.0026 (15)	−0.0105 (15)	0.0000 (16)

Geometric parameters (Å, º)

Mn1—O3^i	2.139 (2)	C2—C16	1.524 (4)
Mn1—O1W	2.141 (3)	C3—C4	1.410 (4)
Mn1—O2W	2.148 (3)	C3—C10	1.496 (4)
Mn1—O1	2.228 (2)	C4—C5	1.502 (4)
Mn1—N1	2.242 (3)	C5—C6	1.386 (5)
Mn1—N3	2.311 (3)	C6—C7	1.383 (5)
N1—C1	1.333 (4)	C6—H6	0.9300
N1—C4	1.335 (4)	C7—C8	1.372 (6)
N2—C2	1.337 (4)	C7—H7	0.9300
N2—C3	1.342 (4)	C8—C9	1.379 (6)
N3—C9	1.345 (4)	C8—H8	0.9300
N3—C5	1.346 (4)	C9—H9	0.9300
N4—C10	1.339 (4)	C10—C11	1.380 (5)
N4—C14	1.341 (4)	C11—C12	1.385 (5)
O1—C15	1.257 (4)	C11—H11	0.9300
O2—C15	1.243 (4)	C12—C13	1.376 (5)
O3—C16	1.254 (4)	C12—H12	0.9300
O3—Mn1^i	2.139 (2)	C13—C14	1.367 (5)
O4—C16	1.239 (4)	C13—H13	0.9300
O1W—H1WA	0.831 (19)	C14—H14	0.9300
O1W—H1WB	0.839 (19)	O3W—H3WA	0.834 (19)
O2W—H2WA	0.841 (19)	O3W—H3WB	0.851 (19)
O2W—H2WB	0.833 (19)	O4W—H4WA	0.84 (2)
C1—C2	1.397 (4)	O4W—H4WB	0.84 (2)
C1—C15	1.524 (4)
O3^i—Mn1—O1W	162.15 (10)	N1—C4—C5	113.8 (3)
O3^i—Mn1—O2W	85.00 (11)	C3—C4—C5	127.3 (3)
O1W—Mn1—O2W	86.92 (12)	N3—C5—C6	121.5 (3)
O3^i—Mn1—O1	89.80 (9)	N3—C5—C4	114.0 (3)
O1W—Mn1—O1	81.62 (10)	C6—C5—C4	124.5 (3)
O2W—Mn1—O1	124.11 (10)	C7—C6—C5	118.9 (3)
O3^i—Mn1—N1	99.80 (10)	C7—C6—H6	120.5
O1W—Mn1—N1	92.39 (11)	C5—C6—H6	120.5
O2W—Mn1—N1	163.62 (11)	C8—C7—C6	119.7 (3)
O1—Mn1—N1	71.84 (8)	C8—C7—H7	120.1
O3^i—Mn1—N3	100.80 (10)	C6—C7—H7	120.1
O1W—Mn1—N3	95.57 (11)	C7—C8—C9	118.3 (3)
O2W—Mn1—N3	93.71 (11)	C7—C8—H8	120.8
O1—Mn1—N3	141.63 (9)	C9—C8—H8	120.8
N1—Mn1—N3	70.05 (9)	N3—C9—C8	122.8 (4)
C1—N1—C4	121.1 (3)	N3—C9—H9	118.6
C1—N1—Mn1	117.1 (2)	C8—C9—H9	118.6
C4—N1—Mn1	121.5 (2)	N4—C10—C11	122.8 (3)
C2—N2—C3	119.7 (3)	N4—C10—C3	116.1 (3)
C9—N3—C5	118.5 (3)	C11—C10—C3	121.1 (3)
C9—N3—Mn1	122.3 (2)	C10—C11—C12	118.7 (3)
C5—N3—Mn1	117.1 (2)	C10—C11—H11	120.7
C10—N4—C14	117.2 (3)	C12—C11—H11	120.7
C15—O1—Mn1	119.75 (19)	C13—C12—C11	119.0 (3)
C16—O3—Mn1^i	145.3 (2)	C13—C12—H12	120.5
Mn1—O1W—H1WA	108 (3)	C11—C12—H12	120.5
Mn1—O1W—H1WB	132 (3)	C14—C13—C12	118.6 (3)
H1WA—O1W—H1WB	105 (4)	C14—C13—H13	120.7
Mn1—O2W—H2WA	118 (3)	C12—C13—H13	120.7
Mn1—O2W—H2WB	121 (3)	N4—C14—C13	123.7 (4)
H2WA—O2W—H2WB	104 (4)	N4—C14—H14	118.1
N1—C1—C2	119.7 (3)	C13—C14—H14	118.1
N1—C1—C15	114.6 (3)	O2—C15—O1	127.1 (3)
C2—C1—C15	125.7 (3)	O2—C15—C1	117.5 (3)
N2—C2—C1	120.2 (3)	O1—C15—C1	115.4 (3)
N2—C2—C16	114.9 (3)	O4—C16—O3	126.5 (3)
C1—C2—C16	124.9 (3)	O4—C16—C2	116.0 (3)
N2—C3—C4	120.3 (3)	O3—C16—C2	117.2 (3)
N2—C3—C10	114.7 (3)	H3WA—O3W—H3WB	108 (5)
C4—C3—C10	124.9 (3)	H4WA—O4W—H4WB	106 (5)
N1—C4—C3	118.8 (3)
C4—N1—C1—C2	2.5 (5)	C5—C6—C7—C8	0.4 (6)
Mn1—N1—C1—C2	176.7 (2)	C6—C7—C8—C9	3.2 (6)
C4—N1—C1—C15	−176.9 (3)	C5—N3—C9—C8	−1.1 (6)
Mn1—N1—C1—C15	−2.7 (3)	Mn1—N3—C9—C8	161.9 (3)
C3—N2—C2—C1	1.2 (5)	C7—C8—C9—N3	−2.9 (7)
C3—N2—C2—C16	179.1 (3)	C14—N4—C10—C11	−1.2 (5)
N1—C1—C2—N2	−3.5 (5)	C14—N4—C10—C3	177.5 (3)
C15—C1—C2—N2	175.8 (3)	N2—C3—C10—N4	−65.6 (4)
N1—C1—C2—C16	178.9 (3)	C4—C3—C10—N4	116.5 (4)
C15—C1—C2—C16	−1.8 (5)	N2—C3—C10—C11	113.1 (3)
C2—N2—C3—C4	1.9 (5)	C4—C3—C10—C11	−64.8 (5)
C2—N2—C3—C10	−176.2 (3)	N4—C10—C11—C12	1.0 (5)
C1—N1—C4—C3	0.6 (5)	C3—C10—C11—C12	−177.6 (3)
Mn1—N1—C4—C3	−173.3 (2)	C10—C11—C12—C13	−0.4 (5)
C1—N1—C4—C5	177.8 (3)	C11—C12—C13—C14	0.2 (6)
Mn1—N1—C4—C5	3.9 (4)	C10—N4—C14—C13	0.9 (6)
N2—C3—C4—N1	−2.8 (5)	C12—C13—C14—N4	−0.4 (6)
C10—C3—C4—N1	175.0 (3)	Mn1—O1—C15—O2	−166.2 (3)
N2—C3—C4—C5	−179.7 (3)	Mn1—O1—C15—C1	12.6 (4)
C10—C3—C4—C5	−1.8 (5)	N1—C1—C15—O2	172.6 (3)
C9—N3—C5—C6	4.9 (5)	C2—C1—C15—O2	−6.7 (5)
Mn1—N3—C5—C6	−158.9 (3)	N1—C1—C15—O1	−6.3 (4)
C9—N3—C5—C4	−174.5 (3)	C2—C1—C15—O1	174.3 (3)
Mn1—N3—C5—C4	21.7 (4)	Mn1^i—O3—C16—O4	−176.0 (3)
N1—C4—C5—N3	−16.8 (4)	Mn1^i—O3—C16—C2	9.6 (5)
C3—C4—C5—N3	160.2 (3)	N2—C2—C16—O4	−77.6 (4)
N1—C4—C5—C6	163.8 (3)	C1—C2—C16—O4	100.2 (4)
C3—C4—C5—C6	−19.2 (6)	N2—C2—C16—O3	97.5 (4)
N3—C5—C6—C7	−4.6 (6)	C1—C2—C16—O3	−84.8 (4)
C4—C5—C6—C7	174.8 (3)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1^ii	0.83 (2)	1.89 (2)	2.710 (4)	168 (4)
O1W—H1WB···N4^iii	0.84 (2)	1.91 (2)	2.750 (4)	179 (5)
O2W—H2WA···O2^ii	0.84 (2)	1.91 (2)	2.743 (4)	170 (5)
O2W—H2WB···O3W^iv	0.83 (2)	1.92 (3)	2.710 (4)	159 (4)
O3W—H3WA···O4W	0.83 (2)	2.08 (2)	2.888 (5)	163 (5)
O3W—H3WB···O4W^v	0.85 (2)	2.07 (2)	2.906 (5)	169 (5)
O4W—H4WA···O4^vi	0.84 (2)	2.16 (2)	3.000 (4)	175 (6)
O4W—H4WB···O4^vii	0.84 (2)	1.95 (2)	2.793 (4)	176 (6)
C7—H7···O3^viii	0.93	2.40	3.216 (5)	147
C8—H8···O2^viii	0.93	2.54	3.452 (4)	167

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

(II) Bis[µ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ⁴N¹,O²,N⁶:O³;κ⁴O³:N¹,O²,N⁶-bis[diaquairon(II)] tetrahydrate

Crystal data

[Fe2(C16H8N4O4)2(H2O)4]·4H2O	Z = 1
Mr = 896.35	F(000) = 460
Triclinic, P1	Dx = 1.655 Mg m^−3
a = 8.0933 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3403 (11) Å	Cell parameters from 5000 reflections
c = 11.5679 (12) Å	θ = 3.3–52.1°
α = 69.500 (12)°	µ = 0.90 mm^−1
β = 83.593 (13)°	T = 223 K
γ = 84.238 (13)°	Block, dark-violet
V = 899.16 (18) Å^3	0.30 × 0.20 × 0.10 mm

Data collection

Stoe IPDS 1 image plate diffractometer	3202 independent reflections
Radiation source: fine-focus sealed tube	2475 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.063
φ rotation scans	θmax = 25.7°, θmin = 2.1°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −9→9
Tmin = 0.805, Tmax = 1.000	k = −12→12
6988 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: mixed
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.072P)^2] where P = (Fo^2 + 2Fc^2)/3
3202 reflections	(Δ/σ)max = 0.001
294 parameters	Δρmax = 0.59 e Å^−3
8 restraints	Δρmin = −0.69 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.

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

	x	y	z	Uiso*/Ueq
Fe1	0.71296 (5)	0.99041 (4)	0.82831 (4)	0.01544 (16)
N1	0.9194 (3)	0.8624 (2)	0.9131 (2)	0.0142 (5)
N2	1.1679 (3)	0.6879 (2)	1.0372 (2)	0.0154 (6)
N3	0.8286 (3)	0.8855 (3)	0.7002 (3)	0.0202 (6)
N4	1.4267 (3)	0.6299 (3)	0.8589 (3)	0.0226 (6)
O1	0.7040 (3)	1.00868 (19)	1.0068 (2)	0.0165 (5)
O2	0.7957 (3)	0.9106 (2)	1.1961 (2)	0.0211 (5)
O3	1.1738 (3)	0.8201 (2)	1.2494 (2)	0.0194 (5)
O4	1.0447 (3)	0.6252 (2)	1.3039 (2)	0.0245 (5)
O1W	0.5488 (3)	0.8329 (2)	0.9222 (2)	0.0225 (5)
H1WA	0.463 (3)	0.863 (4)	0.955 (4)	0.040 (12)*
H1WB	0.508 (6)	0.784 (5)	0.891 (5)	0.078 (18)*
O2W	0.5259 (3)	1.0878 (2)	0.7138 (3)	0.0277 (6)
H2WA	0.423 (3)	1.080 (4)	0.744 (3)	0.028 (10)*
H2WB	0.547 (5)	1.160 (3)	0.654 (3)	0.030 (11)*
C1	0.9344 (3)	0.8476 (3)	1.0307 (3)	0.0123 (6)
C2	1.0637 (4)	0.7604 (3)	1.0931 (3)	0.0137 (6)
C3	1.1487 (4)	0.7011 (3)	0.9199 (3)	0.0151 (7)
C4	1.0221 (4)	0.7921 (3)	0.8542 (3)	0.0139 (6)
C5	0.9805 (4)	0.8186 (3)	0.7251 (3)	0.0182 (7)
C6	1.0827 (4)	0.7811 (3)	0.6371 (3)	0.0254 (8)
H6	1.1908	0.7411	0.6540	0.031*
C7	1.0240 (5)	0.8032 (3)	0.5224 (4)	0.0320 (9)
H7	1.0915	0.7775	0.4614	0.038*
C8	0.8663 (5)	0.8629 (4)	0.4998 (4)	0.0326 (9)
H8	0.8218	0.8744	0.4249	0.039*
C9	0.7745 (5)	0.9057 (3)	0.5888 (3)	0.0292 (8)
H9	0.6690	0.9512	0.5710	0.035*
C10	1.2661 (4)	0.6075 (3)	0.8702 (3)	0.0150 (6)
C11	1.2068 (4)	0.5027 (3)	0.8409 (3)	0.0212 (7)
H11	1.0922	0.4899	0.8496	0.025*
C12	1.3217 (4)	0.4167 (3)	0.7982 (3)	0.0252 (8)
H12	1.2857	0.3450	0.7768	0.030*
C13	1.4882 (4)	0.4381 (3)	0.7877 (3)	0.0268 (8)
H13	1.5685	0.3808	0.7601	0.032*
C14	1.5346 (4)	0.5459 (3)	0.8187 (4)	0.0282 (8)
H14	1.6486	0.5608	0.8111	0.034*
C15	0.8008 (3)	0.9290 (3)	1.0849 (3)	0.0137 (6)
C16	1.0942 (4)	0.7348 (3)	1.2273 (3)	0.0162 (7)
O3W	0.5377 (4)	0.3176 (3)	0.5121 (3)	0.0389 (7)
H3WA	0.448 (4)	0.365 (5)	0.507 (6)	0.08 (2)*
H3WB	0.611 (4)	0.374 (4)	0.500 (4)	0.044 (13)*
O4W	0.2296 (3)	0.4837 (3)	0.5051 (3)	0.0351 (6)
H4WA	0.159 (5)	0.448 (4)	0.564 (3)	0.050 (14)*
H4WB	0.177 (7)	0.527 (6)	0.445 (4)	0.10 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0188 (3)	0.0121 (2)	0.0149 (3)	0.00398 (16)	−0.00588 (18)	−0.00385 (17)
N1	0.0159 (12)	0.0098 (11)	0.0163 (16)	0.0009 (9)	−0.0017 (11)	−0.0042 (10)
N2	0.0175 (13)	0.0114 (11)	0.0181 (16)	0.0014 (9)	−0.0042 (11)	−0.0058 (11)
N3	0.0237 (14)	0.0199 (13)	0.0170 (17)	0.0032 (11)	−0.0073 (12)	−0.0059 (12)
N4	0.0202 (14)	0.0204 (13)	0.0297 (19)	0.0033 (11)	−0.0044 (13)	−0.0124 (12)
O1	0.0200 (11)	0.0132 (9)	0.0166 (13)	0.0053 (8)	−0.0049 (9)	−0.0062 (9)
O2	0.0211 (11)	0.0273 (11)	0.0154 (14)	0.0050 (9)	−0.0034 (10)	−0.0093 (10)
O3	0.0269 (12)	0.0160 (10)	0.0155 (13)	−0.0035 (9)	−0.0053 (10)	−0.0042 (9)
O4	0.0328 (13)	0.0183 (11)	0.0173 (14)	−0.0067 (9)	−0.0059 (11)	0.0028 (10)
O1W	0.0193 (12)	0.0168 (11)	0.0338 (16)	−0.0020 (9)	0.0023 (11)	−0.0128 (11)
O2W	0.0184 (13)	0.0250 (12)	0.0284 (17)	0.0022 (10)	−0.0067 (11)	0.0052 (11)
C1	0.0154 (14)	0.0083 (12)	0.0130 (18)	−0.0002 (11)	−0.0014 (13)	−0.0035 (12)
C2	0.0173 (15)	0.0090 (12)	0.0143 (18)	−0.0028 (11)	−0.0015 (13)	−0.0027 (12)
C3	0.0161 (15)	0.0096 (13)	0.020 (2)	−0.0005 (11)	−0.0012 (13)	−0.0055 (12)
C4	0.0168 (15)	0.0111 (13)	0.0147 (18)	−0.0010 (11)	−0.0004 (13)	−0.0058 (12)
C5	0.0247 (16)	0.0110 (13)	0.018 (2)	0.0022 (12)	−0.0030 (14)	−0.0048 (13)
C6	0.0363 (19)	0.0189 (15)	0.020 (2)	0.0123 (14)	−0.0055 (16)	−0.0077 (14)
C7	0.052 (2)	0.0223 (16)	0.019 (2)	0.0090 (16)	−0.0002 (18)	−0.0073 (15)
C8	0.053 (2)	0.0293 (18)	0.018 (2)	0.0063 (16)	−0.0142 (18)	−0.0112 (16)
C9	0.037 (2)	0.0278 (17)	0.024 (2)	0.0082 (15)	−0.0119 (17)	−0.0110 (16)
C10	0.0209 (15)	0.0111 (13)	0.0108 (18)	0.0028 (11)	−0.0054 (13)	−0.0007 (12)
C11	0.0232 (16)	0.0131 (14)	0.027 (2)	0.0000 (12)	−0.0036 (15)	−0.0058 (14)
C12	0.0371 (19)	0.0139 (14)	0.025 (2)	0.0012 (13)	−0.0041 (16)	−0.0069 (14)
C13	0.0325 (19)	0.0201 (15)	0.027 (2)	0.0112 (14)	−0.0035 (16)	−0.0102 (15)
C14	0.0190 (17)	0.0296 (17)	0.038 (3)	0.0072 (13)	−0.0039 (16)	−0.0166 (17)
C15	0.0140 (14)	0.0110 (13)	0.018 (2)	−0.0007 (11)	−0.0031 (13)	−0.0067 (12)
C16	0.0159 (15)	0.0153 (14)	0.0166 (19)	0.0044 (12)	−0.0041 (13)	−0.0050 (13)
O3W	0.0379 (17)	0.0250 (13)	0.042 (2)	0.0034 (12)	−0.0074 (14)	0.0028 (12)
O4W	0.0258 (14)	0.0379 (15)	0.0308 (19)	−0.0003 (11)	−0.0060 (13)	0.0024 (13)

Geometric parameters (Å, º)

Fe1—O3^i	2.105 (2)	C2—C16	1.525 (4)
Fe1—O1W	2.115 (2)	C3—C4	1.411 (4)
Fe1—O2W	2.066 (2)	C3—C10	1.502 (4)
Fe1—O1	2.131 (2)	C4—C5	1.492 (4)
Fe1—N1	2.126 (2)	C5—C6	1.377 (5)
Fe1—N3	2.205 (3)	C6—C7	1.394 (5)
N1—C1	1.333 (4)	C6—H6	0.9400
N1—C4	1.335 (4)	C7—C8	1.372 (5)
N2—C2	1.335 (4)	C7—H7	0.9400
N2—C3	1.340 (4)	C8—C9	1.374 (5)
N3—C9	1.347 (4)	C8—H8	0.9400
N3—C5	1.357 (4)	C9—H9	0.9400
N4—C10	1.327 (4)	C10—C11	1.385 (4)
N4—C14	1.331 (4)	C11—C12	1.391 (5)
O1—C15	1.271 (4)	C11—H11	0.9400
O2—C15	1.229 (4)	C12—C13	1.373 (5)
O3—C16	1.251 (3)	C12—H12	0.9400
O3—Fe1^i	2.105 (2)	C13—C14	1.381 (5)
O4—C16	1.240 (4)	C13—H13	0.9400
O1W—H1WA	0.836 (19)	C14—H14	0.9400
O1W—H1WB	0.83 (2)	O3W—H3WA	0.83 (2)
O2W—H2WA	0.867 (19)	O3W—H3WB	0.843 (19)
O2W—H2WB	0.840 (19)	O4W—H4WA	0.842 (19)
C1—C2	1.398 (4)	O4W—H4WB	0.82 (2)
C1—C15	1.519 (4)
O3^i—Fe1—O1W	164.77 (9)	N1—C4—C5	113.3 (2)
O3^i—Fe1—O2W	85.22 (9)	C3—C4—C5	128.5 (3)
O1W—Fe1—O2W	87.43 (10)	N3—C5—C6	121.7 (3)
O3^i—Fe1—O1	89.65 (8)	N3—C5—C4	113.3 (3)
O1W—Fe1—O1	82.38 (9)	C6—C5—C4	125.0 (3)
O2W—Fe1—O1	119.49 (10)	C5—C6—C7	119.2 (3)
O3^i—Fe1—N1	99.21 (9)	C5—C6—H6	120.4
O1W—Fe1—N1	91.27 (9)	C7—C6—H6	120.4
O2W—Fe1—N1	165.15 (10)	C8—C7—C6	119.1 (3)
N1—Fe1—O1	74.91 (9)	C8—C7—H7	120.4
O3^i—Fe1—N3	99.60 (9)	C6—C7—H7	120.4
O1W—Fe1—N3	94.03 (10)	C7—C8—C9	118.7 (3)
O2W—Fe1—N3	92.45 (10)	C7—C8—H8	120.6
O1—Fe1—N3	147.49 (9)	C9—C8—H8	120.6
N1—Fe1—N3	72.87 (10)	N3—C9—C8	123.1 (3)
C1—N1—C4	121.5 (2)	N3—C9—H9	118.4
C1—N1—Fe1	116.87 (19)	C8—C9—H9	118.4
C4—N1—Fe1	121.4 (2)	N4—C10—C11	123.0 (3)
C2—N2—C3	119.3 (2)	N4—C10—C3	116.3 (2)
C9—N3—C5	117.9 (3)	C11—C10—C3	120.7 (3)
C9—N3—Fe1	124.0 (2)	C10—C11—C12	118.2 (3)
C5—N3—Fe1	116.9 (2)	C10—C11—H11	120.9
C10—N4—C14	117.9 (3)	C12—C11—H11	120.9
C15—O1—Fe1	118.95 (19)	C13—C12—C11	119.1 (3)
C16—O3—Fe1^i	144.9 (2)	C13—C12—H12	120.4
Fe1—O1W—H1WA	112 (3)	C11—C12—H12	120.4
Fe1—O1W—H1WB	126 (4)	C12—C13—C14	118.2 (3)
H1WA—O1W—H1WB	101 (4)	C12—C13—H13	120.9
Fe1—O2W—H2WA	119 (3)	C14—C13—H13	120.9
Fe1—O2W—H2WB	118 (3)	N4—C14—C13	123.5 (3)
H2WA—O2W—H2WB	117 (4)	N4—C14—H14	118.2
N1—C1—C2	119.6 (3)	C13—C14—H14	118.2
N1—C1—C15	114.3 (2)	O2—C15—O1	127.5 (3)
C2—C1—C15	126.1 (3)	O2—C15—C1	118.4 (2)
N2—C2—C1	120.4 (3)	O1—C15—C1	114.0 (3)
N2—C2—C16	115.0 (2)	O4—C16—O3	126.2 (3)
C1—C2—C16	124.6 (3)	O4—C16—C2	115.5 (2)
N2—C3—C4	121.1 (3)	O3—C16—C2	118.2 (3)
N2—C3—C10	114.3 (2)	H3WA—O3W—H3WB	105 (4)
C4—C3—C10	124.6 (3)	H4WA—O4W—H4WB	107 (5)
N1—C4—C3	118.1 (3)
C4—N1—C1—C2	2.2 (4)	C5—C6—C7—C8	0.6 (5)
Fe1—N1—C1—C2	177.48 (19)	C6—C7—C8—C9	3.4 (5)
C4—N1—C1—C15	−176.6 (2)	C5—N3—C9—C8	−0.6 (5)
Fe1—N1—C1—C15	−1.3 (3)	Fe1—N3—C9—C8	166.1 (3)
C3—N2—C2—C1	1.0 (4)	C7—C8—C9—N3	−3.5 (6)
C3—N2—C2—C16	178.6 (2)	C14—N4—C10—C11	−0.8 (5)
N1—C1—C2—N2	−2.7 (4)	C14—N4—C10—C3	177.9 (3)
C15—C1—C2—N2	176.0 (2)	N2—C3—C10—N4	−65.1 (4)
N1—C1—C2—C16	−180.0 (2)	C4—C3—C10—N4	117.8 (3)
C15—C1—C2—C16	−1.4 (4)	N2—C3—C10—C11	113.7 (3)
C2—N2—C3—C4	1.1 (4)	C4—C3—C10—C11	−63.5 (4)
C2—N2—C3—C10	−176.2 (2)	N4—C10—C11—C12	0.3 (5)
C1—N1—C4—C3	−0.2 (4)	C3—C10—C11—C12	−178.3 (3)
Fe1—N1—C4—C3	−175.24 (19)	C10—C11—C12—C13	0.5 (5)
C1—N1—C4—C5	177.6 (2)	C11—C12—C13—C14	−0.8 (5)
Fe1—N1—C4—C5	2.6 (3)	C10—N4—C14—C13	0.4 (5)
N2—C3—C4—N1	−1.5 (4)	C12—C13—C14—N4	0.3 (6)
C10—C3—C4—N1	175.5 (3)	Fe1—O1—C15—O2	−168.1 (2)
N2—C3—C4—C5	−178.9 (3)	Fe1—O1—C15—C1	10.8 (3)
C10—C3—C4—C5	−2.0 (5)	N1—C1—C15—O2	172.9 (2)
C9—N3—C5—C6	4.8 (4)	C2—C1—C15—O2	−5.8 (4)
Fe1—N3—C5—C6	−162.8 (2)	N1—C1—C15—O1	−6.1 (3)
C9—N3—C5—C4	−175.5 (3)	C2—C1—C15—O1	175.2 (3)
Fe1—N3—C5—C4	16.9 (3)	Fe1^i—O3—C16—O4	180.0 (2)
N1—C4—C5—N3	−12.7 (4)	Fe1^i—O3—C16—C2	4.6 (5)
C3—C4—C5—N3	164.8 (3)	N2—C2—C16—O4	−76.7 (3)
N1—C4—C5—C6	167.0 (3)	C1—C2—C16—O4	100.8 (3)
C3—C4—C5—C6	−15.4 (5)	N2—C2—C16—O3	99.2 (3)
N3—C5—C6—C7	−4.8 (5)	C1—C2—C16—O3	−83.4 (4)
C4—C5—C6—C7	175.5 (3)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1^ii	0.84 (2)	1.93 (2)	2.728 (3)	160 (4)
O1W—H1WB···N4^iii	0.83 (2)	1.94 (2)	2.752 (3)	165 (6)
O2W—H2WA···O2^ii	0.87 (2)	1.83 (2)	2.694 (3)	172 (3)
O2W—H2WB···O3W^iv	0.84 (2)	1.87 (2)	2.686 (4)	165 (4)
O3W—H3WA···O4W	0.83 (2)	2.04 (2)	2.874 (4)	176 (6)
O3W—H3WB···O4W^v	0.84 (2)	2.03 (2)	2.866 (4)	171 (4)
O4W—H4WA···O4^vi	0.84 (2)	2.12 (2)	2.957 (4)	172 (5)
O4W—H4WB···O4^vii	0.82 (2)	1.96 (2)	2.784 (4)	178 (7)
C7—H7···O3^viii	0.94	2.36	3.206 (5)	149
C8—H8···O2^viii	0.94	2.57	3.477 (4)	162

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