catena-Poly[[aqua­(4,4′-bipyridine-κN)manganese(II)]-μ-imidazole-4,5-di­carboxyl­ato-κ⁴N³,O⁴:O^4′,O⁵]

In the crystal structure of the title compound, [Mn(C₅H₂N₂O₄)(C₁₀H₈N₂)(H₂O)]_n, the Mn atom is coordinated by three O atoms, two N atoms and one water mol­ecule in a distorted octa­hedral geometry. Mn atoms are connected via the imidazole-4,5-dicarboxyl­ate anions into chains, which are further connected by inter­molecular N—H...O, O—H...N and O—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.028
• wR factor = 0.074
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

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Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A    ..  O2      ..       2.65 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.11

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

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

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S1. Comment

Investigations on metal carboxylate coordination polymers have become of increasing interest in the past few years Wang et al. 2005; Hao et al. 2005). As a part of our ongoing investigations in this field we report here the crystal structure of the title compound. In the crystal structure of the title compound the Mn atoms are coordinated by one oxygen atom of a water molecule, one nitrogen atom of a 4,4'-bipyridine ligand, one N and one O atom of an imidazole-4,5-dicarboxylate anion and one carboxylate group of a symmetry related imidazole-4,5-dicarboxylate anion within a distorted octahedral coordination geometry (Figure 1). The manganese atoms are linked by the anions into chains that elongate in the direction of the crystallographic b axis. These chains are further connected by N—H···O, O—H···N and O—H···O hydrogen bonding into a three-dimensional network (Tab. 1).

Related literature

For general background, see: Wang et al. (2005). For related structures, see: Hao et al. (2005).

S2. Experimental

A mixture of MnCl₂ (0.5 mmol), imidazole-4,5-dicarboxylic acid (0.5 mmol), 4,4'-bipyridine (0.8 mmol), and water (10 ml) was stirred for 20 min and then transferred into a 23 ml Teflon reactor. The reactor was kept at 433 K for 120 h under autogenous pressure. Single crystals of (I) were obtained after cooling to room temperature.

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.93 Å and N—H = 0.86 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C,N). The H atoms of the water molecule were located in difference map, their bond lengths were set to 0.85 Å and afterwards they were refined using a riding model with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997.

Figures

Fig. 1. Crystal structure of (I) with labeling and displacement ellipsoids drawn at the 50% probability level.

catena-Poly[[aqua(4,4'-bipyridine-κN)manganese(II)]-µ-imidazole-4,5- dicarboxylato-κ⁴N³,O⁴:O^4',O⁵]

Crystal data

[Mn(C5H2N2O4)(C10H8N2)(H2O)]	F(000) = 780
Mr = 383.23	Dx = 1.626 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 14768 reflections
a = 14.051 (3) Å	θ = 3.0–27.5°
b = 8.2084 (16) Å	µ = 0.88 mm^−1
c = 13.979 (3) Å	T = 298 K
β = 103.80 (3)°	Block, colorless
V = 1565.8 (5) Å^3	0.24 × 0.18 × 0.17 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	3585 independent reflections
Radiation source: fine-focus sealed tube	3170 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.817, Tmax = 0.865	k = −10→10
14768 measured reflections	l = −18→17

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.4434P] where P = (Fo^2 + 2Fc^2)/3
3585 reflections	(Δ/σ)max = 0.001
228 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.25 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	0.655818 (15)	0.01342 (3)	0.319366 (15)	0.01988 (8)
C1	0.54650 (12)	0.1764 (2)	0.48789 (11)	0.0298 (3)
H1A	0.5925	0.1506	0.5456	0.036*
C2	0.47557 (10)	0.21157 (17)	0.33523 (10)	0.0205 (3)
C3	0.41124 (11)	0.26685 (17)	0.38842 (10)	0.0218 (3)
C4	0.47212 (10)	0.20023 (17)	0.22797 (10)	0.0211 (3)
C5	0.30854 (11)	0.33264 (18)	0.36474 (11)	0.0240 (3)
C6	0.84725 (13)	0.2004 (2)	0.31644 (14)	0.0353 (4)
H6A	0.8634	0.0935	0.3049	0.042*
C7	0.92054 (13)	0.3157 (2)	0.33212 (14)	0.0349 (4)
H7A	0.9844	0.2855	0.3322	0.042*
C8	0.89897 (12)	0.47683 (18)	0.34779 (12)	0.0280 (3)
C9	0.80176 (14)	0.5129 (2)	0.34472 (18)	0.0451 (5)
H9A	0.7829	0.6197	0.3523	0.054*
C10	0.73332 (13)	0.3891 (2)	0.33030 (17)	0.0432 (5)
H10A	0.6689	0.4156	0.3299	0.052*
C11	1.14620 (13)	0.6796 (2)	0.42065 (14)	0.0407 (4)
H11A	1.2117	0.6482	0.4351	0.049*
C12	1.07570 (13)	0.5603 (2)	0.39433 (14)	0.0383 (4)
H12A	1.0941	0.4518	0.3922	0.046*
C13	0.97745 (12)	0.60229 (19)	0.37104 (12)	0.0292 (3)
C14	0.95562 (14)	0.7667 (2)	0.37459 (17)	0.0446 (5)
H14A	0.8909	0.8023	0.3585	0.054*
C15	1.03154 (15)	0.8763 (2)	0.40235 (17)	0.0497 (5)
H15A	1.0156	0.9860	0.4043	0.060*
N1	0.55941 (9)	0.15294 (16)	0.39850 (9)	0.0250 (3)
N2	0.45860 (10)	0.24189 (17)	0.48485 (9)	0.0277 (3)
H2A	0.4357	0.2645	0.5351	0.033*
N3	0.75455 (10)	0.23313 (16)	0.31690 (10)	0.0302 (3)
N4	1.12591 (11)	0.83635 (19)	0.42656 (12)	0.0411 (4)
O1	0.40748 (8)	0.27583 (13)	0.16630 (7)	0.0267 (2)
O2	0.53640 (9)	0.11390 (15)	0.20466 (7)	0.0329 (3)
O3	0.27564 (8)	0.39872 (14)	0.28237 (8)	0.0289 (2)
O4	0.26300 (9)	0.31810 (17)	0.43017 (9)	0.0432 (3)
O1W	0.75594 (8)	−0.06111 (14)	0.45556 (8)	0.0335 (3)
H1	0.7967	0.0042	0.4908	0.050*
H2	0.7548	−0.1473	0.4890	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01936 (12)	0.02130 (12)	0.01915 (11)	0.00103 (8)	0.00493 (8)	−0.00106 (8)
C1	0.0283 (8)	0.0426 (9)	0.0173 (6)	0.0069 (7)	0.0032 (6)	0.0028 (6)
C2	0.0214 (7)	0.0234 (6)	0.0165 (6)	0.0028 (5)	0.0045 (5)	0.0016 (5)
C3	0.0250 (7)	0.0238 (7)	0.0175 (6)	0.0029 (6)	0.0071 (5)	0.0026 (5)
C4	0.0232 (7)	0.0232 (6)	0.0172 (6)	0.0005 (6)	0.0054 (5)	−0.0007 (5)
C5	0.0251 (7)	0.0238 (7)	0.0258 (7)	0.0045 (6)	0.0115 (6)	0.0046 (6)
C6	0.0365 (9)	0.0250 (7)	0.0482 (10)	−0.0016 (7)	0.0178 (8)	−0.0051 (7)
C7	0.0284 (8)	0.0289 (8)	0.0512 (10)	−0.0011 (7)	0.0171 (7)	−0.0053 (7)
C8	0.0280 (8)	0.0244 (7)	0.0313 (8)	−0.0023 (6)	0.0066 (6)	0.0003 (6)
C9	0.0313 (9)	0.0234 (8)	0.0796 (15)	0.0017 (7)	0.0110 (9)	−0.0024 (8)
C10	0.0252 (8)	0.0297 (8)	0.0738 (13)	0.0008 (7)	0.0100 (8)	−0.0002 (9)
C11	0.0272 (8)	0.0425 (10)	0.0492 (10)	−0.0043 (7)	0.0030 (8)	−0.0037 (8)
C12	0.0318 (9)	0.0300 (8)	0.0515 (10)	−0.0002 (7)	0.0068 (8)	−0.0035 (8)
C13	0.0291 (8)	0.0259 (7)	0.0318 (8)	−0.0026 (6)	0.0061 (6)	−0.0022 (6)
C14	0.0314 (9)	0.0280 (8)	0.0699 (13)	−0.0004 (7)	0.0030 (9)	−0.0051 (9)
C15	0.0438 (11)	0.0262 (8)	0.0734 (14)	−0.0043 (8)	0.0023 (10)	−0.0076 (9)
N1	0.0230 (6)	0.0341 (7)	0.0177 (5)	0.0055 (5)	0.0043 (5)	0.0017 (5)
N2	0.0314 (7)	0.0376 (7)	0.0157 (5)	0.0069 (6)	0.0087 (5)	0.0009 (5)
N3	0.0291 (7)	0.0265 (6)	0.0355 (7)	−0.0035 (5)	0.0084 (6)	0.0009 (6)
N4	0.0371 (8)	0.0382 (8)	0.0434 (8)	−0.0112 (7)	0.0003 (7)	−0.0048 (7)
O1	0.0304 (6)	0.0332 (6)	0.0159 (4)	0.0109 (5)	0.0044 (4)	0.0028 (4)
O2	0.0347 (6)	0.0458 (7)	0.0185 (5)	0.0190 (5)	0.0069 (4)	0.0000 (5)
O3	0.0235 (5)	0.0364 (6)	0.0282 (5)	0.0051 (5)	0.0090 (4)	0.0116 (5)
O4	0.0412 (7)	0.0554 (8)	0.0424 (7)	0.0229 (6)	0.0284 (6)	0.0240 (6)
O1W	0.0351 (6)	0.0305 (6)	0.0281 (5)	−0.0091 (5)	−0.0060 (5)	0.0048 (5)

Geometric parameters (Å, º)

Mn1—O3^i	2.1190 (11)	C7—H7A	0.9300
Mn1—O1W	2.1680 (13)	C8—C9	1.388 (2)
Mn1—O1^i	2.1725 (11)	C8—C13	1.487 (2)
Mn1—O2	2.1870 (13)	C9—C10	1.380 (3)
Mn1—N1	2.2550 (13)	C9—H9A	0.9300
Mn1—N3	2.2805 (14)	C10—N3	1.338 (2)
C1—N1	1.3190 (19)	C10—H10A	0.9300
C1—N2	1.338 (2)	C11—N4	1.325 (3)
C1—H1A	0.9300	C11—C12	1.379 (3)
C2—C3	1.3772 (19)	C11—H11A	0.9300
C2—N1	1.3800 (18)	C12—C13	1.384 (2)
C2—C4	1.4915 (18)	C12—H12A	0.9300
C3—N2	1.3689 (18)	C13—C14	1.387 (2)
C3—C5	1.502 (2)	C14—C15	1.379 (3)
C4—O2	1.2509 (18)	C14—H14A	0.9300
C4—O1	1.2567 (18)	C15—N4	1.329 (3)
C5—O4	1.2409 (18)	C15—H15A	0.9300
C5—O3	1.2569 (18)	N2—H2A	0.8600
C6—N3	1.331 (2)	O1—Mn1^ii	2.1725 (11)
C6—C7	1.377 (2)	O3—Mn1^ii	2.1190 (11)
C6—H6A	0.9300	O1W—H1	0.8499
C7—C8	1.386 (2)	O1W—H2	0.8500
O3^i—Mn1—O1W	99.23 (5)	C9—C8—C13	122.15 (15)
O3^i—Mn1—O1^i	85.68 (4)	C10—C9—C8	119.60 (16)
O1W—Mn1—O1^i	81.94 (4)	C10—C9—H9A	120.2
O3^i—Mn1—O2	93.87 (4)	C8—C9—H9A	120.2
O1W—Mn1—O2	166.88 (5)	N3—C10—C9	123.64 (17)
O1^i—Mn1—O2	98.44 (5)	N3—C10—H10A	118.2
O3^i—Mn1—N1	167.76 (4)	C9—C10—H10A	118.2
O1W—Mn1—N1	93.00 (5)	N4—C11—C12	123.70 (17)
O1^i—Mn1—N1	95.95 (5)	N4—C11—H11A	118.2
O2—Mn1—N1	73.89 (4)	C12—C11—H11A	118.2
O3^i—Mn1—N3	88.03 (5)	C11—C12—C13	119.90 (17)
O1W—Mn1—N3	88.10 (5)	C11—C12—H12A	120.0
O1^i—Mn1—N3	167.21 (5)	C13—C12—H12A	120.0
O2—Mn1—N3	93.08 (5)	C12—C13—C14	116.77 (16)
N1—Mn1—N3	92.56 (5)	C12—C13—C8	121.66 (15)
N1—C1—N2	111.28 (13)	C14—C13—C8	121.52 (15)
N1—C1—H1A	124.4	C15—C14—C13	118.82 (17)
N2—C1—H1A	124.4	C15—C14—H14A	120.6
C3—C2—N1	109.80 (12)	C13—C14—H14A	120.6
C3—C2—C4	134.05 (13)	N4—C15—C14	124.66 (18)
N1—C2—C4	116.14 (12)	N4—C15—H15A	117.7
N2—C3—C2	104.77 (12)	C14—C15—H15A	117.7
N2—C3—C5	119.12 (13)	C1—N1—C2	105.49 (12)
C2—C3—C5	136.00 (13)	C1—N1—Mn1	140.65 (11)
O2—C4—O1	123.34 (13)	C2—N1—Mn1	112.55 (9)
O2—C4—C2	116.41 (12)	C1—N2—C3	108.64 (12)
O1—C4—C2	120.24 (13)	C1—N2—H2A	125.7
O4—C5—O3	125.12 (14)	C3—N2—H2A	125.7
O4—C5—C3	116.12 (13)	C6—N3—C10	116.42 (14)
O3—C5—C3	118.76 (13)	C6—N3—Mn1	116.08 (11)
N3—C6—C7	123.76 (15)	C10—N3—Mn1	126.72 (12)
N3—C6—H6A	118.1	C11—N4—C15	116.11 (16)
C7—C6—H6A	118.1	C4—O1—Mn1^ii	128.66 (9)
C6—C7—C8	119.84 (16)	C4—O2—Mn1	119.87 (9)
C6—C7—H7A	120.1	C5—O3—Mn1^ii	132.84 (10)
C8—C7—H7A	120.1	Mn1—O1W—H1	122.5
C7—C8—C9	116.69 (15)	Mn1—O1W—H2	128.7
C7—C8—C13	121.11 (15)	H1—O1W—H2	107.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^iii	0.86	1.99	2.8002 (17)	156
N2—H2A···O2^iii	0.86	2.65	3.2305 (18)	126
O1W—H1···N4^iv	0.85	1.91	2.7513 (19)	173
O1W—H2···O4^v	0.85	1.85	2.6972 (17)	171

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