Bis(benzimidazolium) diaqua­bis(pyridine-2,4-dicarboxyl­ato-κ²N,O)manganese(II) dihydrate

The asymmetric unit of the title compound, (C₇H₇N₂)₂[Mn(C₇H₃O₄N)₂(H₂O)₂]·2H₂O, contains one half-anion, one cation and one uncoordinated water mol­ecule. The Mn^II atom, lying on a centre of symmetry, is coordinated in a distorted octahedral arrangement by two O atoms and two N atoms of two pyridine-2,4-dicarboxyl­ate and two O atoms of two aqua ligands. In the crystal structure, inter­molecular O—H...O and N—H...O hydrogen bonds and π–π inter­actions link the mol­ecules into a three-dimensional supra­molecular framework.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.129
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

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   0 ALERT level B = Potentially serious problem
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   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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Computing details

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

Bis(benzimidazolium) diaquabis(pyridine-2,4-dicarboxylato-κ²N,O)manganese(II) dihydrate

Crystal data

(C7H7N2)2[Mn(C7H3O4N)2(H2O)2]·2H2O	Z = 1
Mr = 695.50	F(000) = 359
Triclinic, P1	Dx = 1.558 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4882 (18) Å	Cell parameters from 1565 reflections
b = 9.0617 (19) Å	θ = 2.8–27.5°
c = 10.7716 (19) Å	µ = 0.52 mm^−1
α = 96.539 (6)°	T = 294 K
β = 101.032 (6)°	Prism, yellow
γ = 111.508 (5)°	0.25 × 0.20 × 0.10 mm
V = 741.1 (3) Å^3

Data collection

Bruker P4 diffractometer	3336 independent reflections
Radiation source: fine-focus sealed tube	2518 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.882, Tmax = 0.949	k = −11→10
5758 measured reflections	l = −13→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 0.2861P] where P = (Fo^2 + 2Fc^2)/3
3336 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

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	0.5000	0.5000	1.0000	0.03100 (18)
N1	0.2762 (3)	0.5338 (3)	0.87778 (19)	0.0293 (5)
N2	0.5380 (3)	0.7591 (3)	0.5869 (2)	0.0358 (5)
H2A	0.6166	0.7396	0.6371	0.043*
N3	0.3660 (3)	0.7646 (3)	0.4112 (2)	0.0340 (5)
H1A	0.3167	0.7499	0.3306	0.041*
C1	0.2079 (4)	0.9105 (4)	0.5182 (3)	0.0424 (7)
H1B	0.1319	0.9113	0.4439	0.051*
C2	0.3267 (3)	0.8397 (3)	0.5131 (2)	0.0298 (5)
C3	0.4381 (3)	0.8372 (3)	0.6256 (3)	0.0310 (6)
C4	0.4359 (4)	0.9056 (4)	0.7470 (3)	0.0410 (7)
H4A	0.5096	0.9034	0.8221	0.049*
C5	0.3180 (5)	0.9770 (4)	0.7498 (3)	0.0499 (8)
H5A	0.3124	1.0249	0.8290	0.060*
C6	0.2083 (4)	0.9793 (4)	0.6384 (4)	0.0531 (9)
H6A	0.1314	1.0294	0.6450	0.064*
C7	0.4923 (4)	0.7194 (3)	0.4593 (3)	0.0383 (6)
H7A	0.5424	0.6668	0.4101	0.046*
C8	0.0067 (3)	0.6130 (3)	0.7543 (2)	0.0270 (5)
C9	0.0775 (3)	0.6628 (3)	0.8871 (2)	0.0276 (5)
H9A	0.0356	0.7240	0.9364	0.033*
C10	0.2101 (3)	0.6208 (3)	0.9453 (2)	0.0259 (5)
C11	0.2063 (4)	0.4837 (3)	0.7502 (2)	0.0338 (6)
H11A	0.2502	0.4227	0.7028	0.041*
C12	0.0712 (4)	0.5196 (3)	0.6867 (2)	0.0331 (6)
H12A	0.0240	0.4807	0.5983	0.040*
C13	0.2878 (3)	0.6649 (3)	1.0904 (2)	0.0274 (5)
C14	−0.1358 (3)	0.6591 (3)	0.6849 (2)	0.0309 (6)
O1	−0.1882 (3)	0.7465 (2)	0.75482 (18)	0.0386 (5)
O2	−0.1924 (3)	0.6113 (3)	0.56707 (18)	0.0461 (5)
O3	0.2246 (2)	0.7398 (2)	1.15757 (16)	0.0360 (5)
O4	0.4100 (2)	0.6229 (2)	1.13554 (16)	0.0342 (4)
O5	0.6890 (3)	0.7362 (3)	0.9736 (2)	0.0399 (5)
H5C	0.732 (5)	0.733 (4)	0.901 (4)	0.070 (12)*
H5B	0.785 (6)	0.781 (5)	1.035 (4)	0.071 (13)*
O6	1.0010 (3)	0.9022 (3)	1.1599 (3)	0.0575 (7)
H6B	1.070 (7)	0.871 (6)	1.159 (5)	0.103 (18)*
H6C	1.053 (6)	1.011 (6)	1.174 (4)	0.094 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0293 (3)	0.0426 (4)	0.0278 (3)	0.0237 (3)	0.0045 (2)	0.0056 (2)
N1	0.0285 (11)	0.0407 (12)	0.0238 (11)	0.0203 (10)	0.0059 (9)	0.0051 (9)
N2	0.0320 (12)	0.0441 (14)	0.0362 (13)	0.0218 (11)	0.0046 (10)	0.0105 (10)
N3	0.0343 (12)	0.0412 (13)	0.0252 (11)	0.0167 (10)	0.0034 (9)	0.0028 (9)
C1	0.0342 (16)	0.0508 (18)	0.0482 (17)	0.0234 (14)	0.0074 (13)	0.0158 (14)
C2	0.0260 (13)	0.0319 (13)	0.0301 (13)	0.0104 (11)	0.0051 (10)	0.0078 (11)
C3	0.0272 (13)	0.0354 (14)	0.0317 (14)	0.0130 (11)	0.0077 (11)	0.0097 (11)
C4	0.0431 (17)	0.0429 (17)	0.0311 (15)	0.0106 (13)	0.0094 (13)	0.0065 (12)
C5	0.058 (2)	0.0451 (18)	0.0482 (19)	0.0174 (16)	0.0288 (17)	0.0021 (14)
C6	0.050 (2)	0.054 (2)	0.071 (2)	0.0319 (17)	0.0258 (18)	0.0146 (17)
C7	0.0374 (16)	0.0406 (16)	0.0418 (16)	0.0202 (13)	0.0135 (13)	0.0050 (13)
C8	0.0244 (12)	0.0296 (13)	0.0272 (13)	0.0124 (10)	0.0038 (10)	0.0056 (10)
C9	0.0279 (13)	0.0353 (14)	0.0241 (12)	0.0180 (11)	0.0065 (10)	0.0048 (10)
C10	0.0248 (12)	0.0325 (13)	0.0223 (12)	0.0139 (11)	0.0051 (10)	0.0060 (10)
C11	0.0401 (15)	0.0441 (16)	0.0241 (13)	0.0262 (13)	0.0076 (11)	0.0020 (11)
C12	0.0361 (15)	0.0459 (16)	0.0202 (12)	0.0223 (13)	0.0039 (11)	0.0036 (11)
C13	0.0272 (13)	0.0321 (13)	0.0247 (12)	0.0150 (11)	0.0048 (10)	0.0043 (10)
C14	0.0306 (14)	0.0341 (14)	0.0314 (14)	0.0167 (11)	0.0056 (11)	0.0105 (11)
O1	0.0389 (11)	0.0543 (13)	0.0338 (10)	0.0313 (10)	0.0075 (9)	0.0107 (9)
O2	0.0482 (13)	0.0622 (14)	0.0292 (11)	0.0328 (11)	−0.0056 (9)	0.0029 (9)
O3	0.0395 (11)	0.0493 (12)	0.0253 (9)	0.0283 (10)	0.0055 (8)	−0.0012 (8)
O4	0.0344 (10)	0.0483 (11)	0.0241 (9)	0.0260 (9)	0.0005 (8)	0.0027 (8)
O5	0.0363 (12)	0.0458 (12)	0.0395 (12)	0.0172 (10)	0.0124 (10)	0.0087 (10)
O6	0.0433 (14)	0.0534 (16)	0.0750 (17)	0.0267 (13)	0.0085 (12)	−0.0057 (13)

Geometric parameters (Å, º)

Mn1—O4^i	2.1534 (17)	C5—C6	1.379 (5)
Mn1—O4	2.1534 (17)	C5—H5A	0.9300
Mn1—N1^i	2.235 (2)	C6—H6A	0.9300
Mn1—N1	2.235 (2)	C7—H7A	0.9300
Mn1—O5^i	2.243 (2)	C8—C12	1.378 (3)
Mn1—O5	2.243 (2)	C8—C9	1.392 (3)
N1—C11	1.339 (3)	C8—C14	1.514 (3)
N1—C10	1.348 (3)	C9—C10	1.380 (3)
N2—C7	1.323 (4)	C9—H9A	0.9300
N2—C3	1.379 (3)	C10—C13	1.519 (3)
N2—H2A	0.8600	C11—C12	1.383 (3)
N3—C7	1.321 (3)	C11—H11A	0.9300
N3—C2	1.384 (3)	C12—H12A	0.9300
N3—H1A	0.8600	C13—O3	1.255 (3)
C1—C6	1.370 (5)	C13—O4	1.263 (3)
C1—C2	1.385 (3)	C14—O2	1.232 (3)
C1—H1B	0.9300	C14—O1	1.281 (3)
C2—C3	1.395 (4)	O5—H5C	0.93 (4)
C3—C4	1.389 (4)	O5—H5B	0.87 (4)
C4—C5	1.379 (4)	O6—H6B	0.74 (5)
C4—H4A	0.9300	O6—H6C	0.90 (5)
O4^i—Mn1—O4	180.00 (7)	C4—C5—H5A	119.1
O4^i—Mn1—N1^i	75.73 (7)	C1—C6—C5	122.6 (3)
O4—Mn1—N1^i	104.27 (7)	C1—C6—H6A	118.7
O4^i—Mn1—N1	104.27 (7)	C5—C6—H6A	118.7
O4—Mn1—N1	75.73 (7)	N3—C7—N2	110.8 (2)
N1^i—Mn1—N1	180.000 (1)	N3—C7—H7A	124.6
O4^i—Mn1—O5^i	91.45 (8)	N2—C7—H7A	124.6
O4—Mn1—O5^i	88.55 (8)	C12—C8—C9	117.7 (2)
N1^i—Mn1—O5^i	90.88 (8)	C12—C8—C14	120.5 (2)
N1—Mn1—O5^i	89.12 (8)	C9—C8—C14	121.8 (2)
O4^i—Mn1—O5	88.55 (8)	C10—C9—C8	119.6 (2)
O4—Mn1—O5	91.45 (8)	C10—C9—H9A	120.2
N1^i—Mn1—O5	89.12 (8)	C8—C9—H9A	120.2
N1—Mn1—O5	90.88 (8)	N1—C10—C9	122.3 (2)
O5^i—Mn1—O5	180.0	N1—C10—C13	115.35 (19)
C11—N1—C10	118.1 (2)	C9—C10—C13	122.3 (2)
C11—N1—Mn1	128.86 (16)	N1—C11—C12	122.3 (2)
C10—N1—Mn1	113.01 (15)	N1—C11—H11A	118.8
C7—N2—C3	108.3 (2)	C12—C11—H11A	118.8
C7—N2—O1^ii	129.05 (17)	C8—C12—C11	120.0 (2)
C3—N2—O1^ii	121.83 (17)	C8—C12—H12A	120.0
C7—N2—H2A	125.8	C11—C12—H12A	120.0
C3—N2—H2A	125.8	O3—C13—O4	124.4 (2)
C7—N3—C2	108.0 (2)	O3—C13—C10	117.4 (2)
C7—N3—O3^iii	126.61 (18)	O4—C13—C10	118.2 (2)
C2—N3—O3^iii	125.17 (16)	O2—C14—O1	124.9 (2)
C7—N3—H1A	126.0	O2—C14—C8	118.5 (2)
C2—N3—H1A	126.0	O1—C14—C8	116.6 (2)
C6—C1—C2	116.5 (3)	C13—O4—Mn1	117.45 (15)
C6—C1—H1B	121.7	Mn1—O5—O1^ii	119.38 (10)
C2—C1—H1B	121.7	Mn1—O5—O6	119.15 (11)
N3—C2—C1	132.4 (2)	O1^ii—O5—O6	99.95 (10)
N3—C2—C3	106.5 (2)	Mn1—O5—H5C	117 (2)
C1—C2—C3	121.1 (2)	O6—O5—H5C	99 (2)
N2—C3—C4	131.8 (3)	Mn1—O5—H5B	115 (3)
N2—C3—C2	106.3 (2)	O1^ii—O5—H5B	102 (3)
C4—C3—C2	121.9 (2)	H5C—O5—H5B	102 (3)
C5—C4—C3	116.1 (3)	O3^ii—O6—O1^iv	113.10 (10)
C5—C4—H4A	122.0	O1^iv—O6—H6B	105 (4)
C3—C4—H4A	122.0	O3^ii—O6—H6C	116 (3)
C6—C5—C4	121.8 (3)	H6B—O6—H6C	107 (5)
C6—C5—H5A	119.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^ii	0.86	1.86	2.705 (3)	167
N3—H1A···O3^iii	0.86	1.86	2.713 (3)	174
O5—H5C···O1^ii	0.93 (4)	1.83 (4)	2.751 (3)	174 (3)
O5—H5B···O6	0.87 (4)	1.90 (4)	2.767 (4)	173 (4)
O6—H6B···O3^ii	0.74 (5)	2.07 (5)	2.797 (3)	169 (5)
O6—H6C···O1^iv	0.90 (5)	2.04 (5)	2.927 (4)	168 (4)

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