catena-Poly[[tetra­aqua­manganese(II)]-μ-6,6′-dihydr­oxy-3,3-diazenediyldibenzoato-κ²O:O′]

In the title compound, [Mn(C₁₄H₈N₂O₆)₂(H₂O)₄]_n, each 6,6′-dihydr­oxy-3,3-diazenediyldibenzoate ligand acts as a carboxyl­ate bridge, leading to the formation of polymeric chains running in the [110] direction. The Mn atom is hexa­coordinated in a distorted octa­hedral geometry by six O atoms [Mn—O = 2.1412 (16)–2.2262 (17) Å] from two organic ligands and four water mol­ecules. The crystal packing is stabilized by π–π inter­actions and inter­molecular O—H...O and O—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.070
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mn1
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.33
           From the CIF: _reflns_number_total               3620
           Count of symmetry unique reflns         2410
           Completeness (_total/calc)            150.21%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1210
           Fraction of Friedel pairs measured     0.502
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

catena-Poly[[tetraaquamanganese(II)]-µ-6,6'-dihydroxy-3,3- diazenediyldibenzoato-κ²O:O']

Crystal data

[Mn(C14H8N2O6)2(H2O)4]	Dx = 1.758 Mg m^−3
Mr = 427.23	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 935 reflections
Hall symbol: P 4nw 2abw	θ = 2.1–26°
a = 10.2694 (13) Å	µ = 0.88 mm^−1
c = 30.611 (8) Å	T = 293 K
V = 3228.2 (10) Å^3	Block, orange
Z = 8	0.18 × 0.14 × 0.12 mm
F(000) = 1752

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3620 independent reflections
Radiation source: fine-focus sealed tube	3153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→13
Tmin = 0.86, Tmax = 0.90	k = −11→12
18659 measured reflections	l = −38→39

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0368P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
3620 reflections	Δρmax = 0.30 e Å^−3
239 parameters	Δρmin = −0.42 e Å^−3
12 restraints	Absolute structure: Flack (1983), 1210 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.003 (16)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Mn1	0.31207 (3)	0.96108 (3)	0.142844 (10)	0.02553 (9)
O1W	0.33240 (17)	0.80000 (17)	0.09491 (5)	0.0435 (4)
H1WA	0.3895	0.8146	0.0755	0.065*
H1WB	0.2693	0.7577	0.0841	0.065*
O2	1.11938 (17)	0.24608 (17)	0.14725 (5)	0.0405 (4)
O2W	0.50673 (16)	1.02057 (18)	0.12576 (6)	0.0462 (4)
H2WA	0.5424	1.0932	0.1199	0.069*
H2WB	0.5549	0.9782	0.1433	0.069*
O3	0.35369 (17)	0.84367 (17)	0.28231 (5)	0.0430 (4)
H3A	0.3428	0.8720	0.2575	0.052*
O3W	0.23079 (16)	1.07358 (16)	0.09064 (5)	0.0415 (4)
H3WA	0.1925	1.1409	0.1003	0.062*
H3WB	0.2401	1.0792	0.0632	0.062*
O4	0.39386 (15)	0.86759 (16)	0.19998 (5)	0.0334 (4)
O4W	0.12448 (17)	0.85805 (19)	0.15441 (5)	0.0442 (4)
H4WA	0.1314	0.8099	0.1769	0.066*
H4WB	0.0908	0.8144	0.1337	0.066*
O5	0.57627 (16)	0.78864 (16)	0.17102 (5)	0.0357 (4)
O6	1.18617 (17)	0.06247 (16)	0.26542 (5)	0.0428 (4)
H6A	1.2242	0.0549	0.2420	0.051*
N1	0.80204 (18)	0.44061 (18)	0.25395 (6)	0.0302 (4)
N2	0.74338 (18)	0.47035 (18)	0.28867 (6)	0.0293 (4)
O1	1.23776 (16)	0.10721 (15)	0.18662 (5)	0.0341 (4)
C2	0.4791 (2)	0.6890 (2)	0.32062 (7)	0.0329 (5)
H2B	0.4319	0.7073	0.3458	0.039*
C3	1.0101 (2)	0.1727 (2)	0.29780 (7)	0.0321 (5)
H3B	1.0209	0.1222	0.3227	0.038*
C4	1.0720 (2)	0.2238 (2)	0.22317 (7)	0.0262 (5)
C5	0.4507 (2)	0.7540 (2)	0.28193 (7)	0.0279 (5)
C6	0.8987 (2)	0.3420 (2)	0.25912 (7)	0.0273 (5)
C7	0.6465 (2)	0.5676 (2)	0.28398 (7)	0.0267 (5)
C8	0.4969 (2)	0.7982 (2)	0.20195 (7)	0.0270 (5)
C9	0.6194 (2)	0.6342 (2)	0.24557 (7)	0.0256 (5)
H9A	0.6672	0.6156	0.2205	0.031*
C10	1.0906 (2)	0.1525 (2)	0.26152 (7)	0.0286 (5)
C11	0.9760 (2)	0.3190 (2)	0.22291 (7)	0.0281 (5)
H11A	0.9634	0.3685	0.1978	0.034*
C12	0.5227 (2)	0.72763 (19)	0.24386 (7)	0.0245 (4)
C13	0.5760 (2)	0.5984 (2)	0.32171 (7)	0.0309 (5)
H13A	0.5956	0.5565	0.3478	0.037*
C14	0.9156 (2)	0.2664 (2)	0.29672 (7)	0.0295 (5)
H14A	0.8626	0.2799	0.3209	0.035*
C1	1.1470 (2)	0.1928 (2)	0.18252 (7)	0.0295 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02670 (18)	0.02635 (17)	0.02353 (15)	0.00340 (14)	0.00019 (14)	0.00063 (13)
O1W	0.0451 (10)	0.0418 (10)	0.0435 (10)	−0.0039 (9)	0.0007 (9)	−0.0126 (8)
O2	0.0487 (10)	0.0430 (10)	0.0297 (8)	0.0185 (8)	0.0010 (8)	0.0022 (8)
O2W	0.0319 (9)	0.0515 (11)	0.0551 (10)	−0.0063 (8)	−0.0049 (8)	0.0242 (9)
O3	0.0428 (10)	0.0523 (11)	0.0339 (9)	0.0268 (8)	0.0079 (8)	0.0098 (8)
O3W	0.0503 (11)	0.0448 (10)	0.0294 (8)	0.0176 (8)	0.0027 (8)	0.0078 (7)
O4	0.0276 (9)	0.0396 (9)	0.0329 (8)	0.0110 (7)	−0.0002 (7)	0.0075 (7)
O4W	0.0436 (11)	0.0535 (12)	0.0354 (9)	−0.0154 (8)	0.0018 (8)	0.0044 (8)
O5	0.0366 (9)	0.0410 (10)	0.0294 (8)	0.0112 (7)	0.0065 (7)	0.0065 (7)
O6	0.0497 (11)	0.0449 (10)	0.0337 (9)	0.0282 (9)	−0.0025 (8)	0.0025 (8)
N1	0.0286 (10)	0.0312 (10)	0.0309 (9)	0.0076 (8)	0.0031 (8)	0.0036 (8)
N2	0.0299 (10)	0.0277 (10)	0.0303 (10)	0.0062 (8)	0.0014 (8)	0.0020 (8)
O1	0.0347 (9)	0.0336 (9)	0.0340 (8)	0.0149 (7)	−0.0032 (7)	−0.0074 (7)
C2	0.0344 (12)	0.0373 (12)	0.0269 (11)	0.0101 (11)	0.0039 (9)	−0.0005 (10)
C3	0.0362 (12)	0.0326 (13)	0.0274 (11)	0.0051 (10)	−0.0051 (9)	0.0056 (9)
C4	0.0252 (11)	0.0242 (11)	0.0292 (11)	0.0018 (8)	−0.0053 (9)	−0.0040 (9)
C5	0.0280 (11)	0.0267 (11)	0.0292 (11)	0.0063 (9)	−0.0003 (9)	−0.0004 (9)
C6	0.0244 (11)	0.0261 (12)	0.0315 (12)	0.0041 (9)	−0.0040 (9)	0.0005 (9)
C7	0.0240 (11)	0.0262 (11)	0.0299 (12)	0.0049 (9)	−0.0009 (9)	0.0007 (9)
C8	0.0283 (11)	0.0231 (11)	0.0296 (11)	0.0008 (9)	−0.0017 (9)	−0.0010 (9)
C9	0.0233 (11)	0.0274 (11)	0.0262 (11)	0.0003 (9)	0.0028 (9)	0.0008 (9)
C10	0.0299 (12)	0.0244 (12)	0.0314 (12)	0.0061 (9)	−0.0059 (9)	−0.0027 (9)
C11	0.0287 (11)	0.0286 (11)	0.0270 (10)	0.0038 (9)	−0.0003 (9)	0.0026 (9)
C12	0.0244 (11)	0.0228 (11)	0.0263 (11)	0.0012 (8)	−0.0009 (9)	0.0008 (8)
C13	0.0376 (13)	0.0331 (12)	0.0220 (11)	0.0065 (10)	−0.0006 (9)	0.0028 (9)
C14	0.0263 (11)	0.0330 (12)	0.0292 (11)	0.0010 (9)	0.0004 (9)	−0.0016 (10)
C1	0.0307 (12)	0.0273 (11)	0.0304 (11)	0.0026 (9)	−0.0030 (9)	−0.0037 (10)

Geometric parameters (Å, º)

Mn1—O3W	2.1412 (16)	N2—C7	1.417 (3)
Mn1—O1^i	2.1517 (15)	O1—C1	1.287 (3)
Mn1—O2W	2.1547 (17)	O1—Mn1^ii	2.1517 (15)
Mn1—O4	2.1648 (15)	C2—C13	1.363 (3)
Mn1—O1W	2.2209 (18)	C2—C5	1.391 (3)
Mn1—O4W	2.2262 (17)	C2—H2B	0.9300
O1W—H1WA	0.8486	C3—C14	1.367 (3)
O1W—H1WB	0.8482	C3—C10	1.400 (3)
O2—C1	1.243 (3)	C3—H3B	0.9300
O2W—H2WA	0.8499	C4—C11	1.388 (3)
O2W—H2WB	0.8498	C4—C10	1.397 (3)
O3—C5	1.357 (3)	C4—C1	1.498 (3)
O3—H3A	0.8200	C5—C12	1.407 (3)
O3W—H3WA	0.8490	C6—C11	1.384 (3)
O3W—H3WB	0.8486	C6—C14	1.399 (3)
O4—C8	1.277 (3)	C7—C9	1.388 (3)
O4W—H4WA	0.8500	C7—C13	1.399 (3)
O4W—H4WB	0.8500	C8—C12	1.497 (3)
O5—C8	1.253 (3)	C9—C12	1.381 (3)
O6—C10	1.353 (3)	C9—H9A	0.9300
O6—H6A	0.8200	C11—H11A	0.9300
N1—N2	1.259 (3)	C13—H13A	0.9300
N1—C6	1.427 (3)	C14—H14A	0.9300
O3W—Mn1—O1^i	87.15 (6)	C10—C3—H3B	119.8
O3W—Mn1—O2W	91.58 (7)	C11—C4—C10	118.2 (2)
O1^i—Mn1—O2W	106.40 (7)	C11—C4—C1	120.68 (19)
O3W—Mn1—O4	173.45 (6)	C10—C4—C1	121.04 (19)
O1^i—Mn1—O4	86.77 (6)	O3—C5—C2	118.23 (19)
O2W—Mn1—O4	87.81 (6)	O3—C5—C12	121.60 (19)
O3W—Mn1—O1W	86.88 (6)	C2—C5—C12	120.2 (2)
O1^i—Mn1—O1W	164.63 (7)	C11—C6—C14	119.5 (2)
O2W—Mn1—O1W	87.92 (7)	C11—C6—N1	115.57 (19)
O4—Mn1—O1W	99.61 (6)	C14—C6—N1	124.8 (2)
O3W—Mn1—O4W	92.17 (7)	C9—C7—C13	119.0 (2)
O1^i—Mn1—O4W	85.73 (7)	C9—C7—N2	125.02 (19)
O2W—Mn1—O4W	167.47 (7)	C13—C7—N2	116.00 (19)
O4—Mn1—O4W	89.80 (6)	O5—C8—O4	123.2 (2)
O1W—Mn1—O4W	80.36 (6)	O5—C8—C12	119.60 (19)
Mn1—O1W—H1WA	113.4	O4—C8—C12	117.21 (19)
Mn1—O1W—H1WB	124.6	C12—C9—C7	121.22 (19)
H1WA—O1W—H1WB	110.1	C12—C9—H9A	119.4
Mn1—O2W—H2WA	134.4	C7—C9—H9A	119.4
Mn1—O2W—H2WB	104.0	O6—C10—C4	122.1 (2)
H2WA—O2W—H2WB	109.4	O6—C10—C3	117.4 (2)
C5—O3—H3A	109.5	C4—C10—C3	120.5 (2)
Mn1—O3W—H3WA	111.1	C6—C11—C4	121.5 (2)
Mn1—O3W—H3WB	137.1	C6—C11—H11A	119.2
H3WA—O3W—H3WB	110.0	C4—C11—H11A	119.2
C8—O4—Mn1	127.37 (14)	C9—C12—C5	118.70 (19)
Mn1—O4W—H4WA	109.5	C9—C12—C8	119.74 (19)
Mn1—O4W—H4WB	118.9	C5—C12—C8	121.57 (18)
H4WA—O4W—H4WB	109.3	C2—C13—C7	120.8 (2)
C10—O6—H6A	109.5	C2—C13—H13A	119.6
N2—N1—C6	114.29 (18)	C7—C13—H13A	119.6
N1—N2—C7	114.91 (18)	C3—C14—C6	119.9 (2)
C1—O1—Mn1^ii	132.24 (14)	C3—C14—H14A	120.1
C13—C2—C5	120.1 (2)	C6—C14—H14A	120.1
C13—C2—H2B	119.9	O2—C1—O1	123.4 (2)
C5—C2—H2B	119.9	O2—C1—C4	120.68 (19)
C14—C3—C10	120.3 (2)	O1—C1—C4	115.89 (19)
C14—C3—H3B	119.8

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H4WA···O3^iii	0.85	2.11	2.930 (3)	162
O4W—H4WB···O5^iv	0.85	1.99	2.801 (2)	160
O3W—H3WA···O2^i	0.85	1.95	2.729 (2)	153
O3—H3A···O4	0.82	1.84	2.566 (2)	147
O3W—H3WB···N1^iv	0.85	2.16	2.990 (3)	166
O2W—H2WA···O2^iv	0.85	1.90	2.753 (3)	176
O2W—H2WB···O5	0.85	2.13	2.846 (3)	141
O6—H6A···O1	0.82	1.78	2.512 (2)	147
O1W—H1WB···O5^iv	0.85	2.04	2.826 (3)	153
O1W—H1WA···O6^v	0.85	2.32	2.907 (2)	127

Symmetry codes: (i) x−1, y+1, z; (iii) −y+1, −x+1, −z+1/2; (iv) x−1/2, −y+3/2, −z+1/4; (v) −y+1/2, x−1/2, z−1/4.