A two-dimensional coordination polymer containing copper(II): poly­[[(1H-benz­imidazole-κN³)copper(II)]-μ₃-3-carboxylato­phenoxy­acetato-κ⁴O,O′:O′′:O′′′]

In the title two-dimensional coordination polymer, [Cu(C₉H₆O₅)(C₇H₆N₂)]_n, each Cu^II atom exists in a distorted square-pyramidal coordination environment, defined by one N atom from the terminal benz­imidazole mol­ecule and four carboxyl O atoms derived from three different 3-carboxyl­ato­phenoxy­acetate (3-CPOA) dianions. The tetradentate 3-CPOA ligand forms three bonds to adjacent Cu atoms to form chains that are linked to neighboring chains, via a fourth Cu—O bond, so as to form a layer structure that is further stabilized by hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.041
• wR factor = 0.102
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H17    ..  O4      ..       2.64 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio

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           27.60
           From the CIF: _reflns_number_total               3313
           Count of symmetry unique reflns         1927
           Completeness (_total/calc)            171.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1386
           Fraction of Friedel pairs measured     0.719
           Are heavy atom types Z>Si present          yes

   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

   0 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

poly[[(1H-benzimidazole-κN³)copper(II)]-µ₃-(3-carboxylatophenoxyacetato- κ⁴O,O':O'':O''')]

Crystal data

[Cu(C9H6O5)(C7H6N2)]	F(000) = 3056
Mr = 375.83	Dx = 1.681 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 11649 reflections
a = 29.0545 (14) Å	θ = 3.4–27.5°
b = 42.7251 (15) Å	µ = 1.50 mm^−1
c = 4.784 (1) Å	T = 293 K
V = 5938.7 (13) Å^3	Prism, blue
Z = 16	0.37 × 0.25 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3313 independent reflections
Radiation source: fine-focus sealed tube	2841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 10 pixels mm^-1	θmax = 27.6°, θmin = 3.2°
ω scan	h = −37→37
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −51→54
Tmin = 0.644, Tmax = 0.764	l = −6→5
12860 measured reflections

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 8.324P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3313 reflections	Δρmax = 0.49 e Å^−3
217 parameters	Δρmin = −0.69 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1386 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (18)

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

	x	y	z	Uiso*/Ueq
Cu1	0.478707 (14)	0.102659 (10)	0.80838 (11)	0.03642 (13)
N1	0.54201 (10)	0.09679 (7)	0.6743 (7)	0.0374 (7)
N2	0.61404 (10)	0.10900 (8)	0.5795 (8)	0.0452 (8)
O1	0.46098 (9)	0.12506 (7)	0.3872 (6)	0.0436 (6)
O2	0.49333 (9)	0.14170 (7)	−0.0055 (5)	0.0421 (7)
O3	0.49748 (9)	0.20063 (6)	0.1931 (7)	0.0448 (7)
O4	0.65983 (9)	0.15110 (6)	0.1346 (6)	0.0434 (7)
O5	0.70130 (9)	0.18858 (7)	−0.0329 (7)	0.0517 (8)
C1	0.57664 (12)	0.11512 (10)	0.7325 (9)	0.0419 (9)
C2	0.60365 (12)	0.08447 (9)	0.4038 (8)	0.0402 (9)
C3	0.62893 (15)	0.06884 (11)	0.2028 (10)	0.0519 (11)
C4	0.60752 (15)	0.04489 (11)	0.0662 (11)	0.0568 (11)
C5	0.56219 (17)	0.03687 (11)	0.1258 (10)	0.0586 (12)
C6	0.53637 (14)	0.05244 (10)	0.3234 (11)	0.0504 (10)
C7	0.55780 (12)	0.07673 (9)	0.4633 (8)	0.0379 (8)
C8	0.48118 (11)	0.14480 (9)	0.2473 (8)	0.0335 (9)
C9	0.49085 (13)	0.17598 (9)	0.3852 (8)	0.0410 (9)
C10	0.53981 (12)	0.20586 (8)	0.0774 (9)	0.0364 (7)
C11	0.54136 (14)	0.23123 (9)	−0.1035 (9)	0.0439 (9)
C12	0.58188 (15)	0.23949 (10)	−0.2315 (11)	0.0519 (11)
C13	0.62186 (13)	0.22275 (9)	−0.1832 (11)	0.0481 (9)
C14	0.62033 (12)	0.19735 (8)	−0.0054 (8)	0.0373 (9)
C15	0.57900 (12)	0.18855 (8)	0.1247 (8)	0.0355 (8)
C16	0.66222 (12)	0.17833 (8)	0.0374 (9)	0.0380 (8)
H1	0.5754	0.1308	0.8667	0.050*
H3	0.6592	0.0744	0.1625	0.062*
H4	0.6235	0.0337	−0.0694	0.068*
H5	0.5488	0.0204	0.0286	0.070*
H6	0.5060	0.0469	0.3607	0.061*
H9A	0.4653	0.1812	0.5070	0.049*
H9B	0.5182	0.1740	0.5005	0.049*
H11	0.5148	0.2427	−0.1382	0.053*
H12	0.5824	0.2565	−0.3523	0.062*
H13	0.6493	0.2285	−0.2690	0.058*
H15	0.5781	0.1712	0.2417	0.043*
H17	0.6400	0.1187	0.5891	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02450 (18)	0.0415 (2)	0.0432 (2)	−0.00406 (18)	0.00592 (18)	−0.0021 (2)
N1	0.0244 (14)	0.0429 (17)	0.0447 (18)	0.0003 (12)	0.0046 (13)	−0.0033 (15)
N2	0.0246 (14)	0.0536 (18)	0.057 (2)	−0.0036 (12)	0.0045 (14)	−0.0023 (19)
O1	0.0374 (14)	0.0515 (16)	0.0417 (15)	−0.0078 (12)	−0.0041 (11)	0.0088 (13)
O2	0.0351 (13)	0.0497 (15)	0.0417 (17)	−0.0087 (12)	0.0105 (11)	−0.0046 (13)
O3	0.0321 (13)	0.0387 (14)	0.0636 (18)	0.0077 (11)	0.0082 (12)	0.0023 (13)
O4	0.0312 (13)	0.0428 (15)	0.056 (2)	0.0064 (11)	0.0089 (11)	0.0101 (14)
O5	0.0298 (13)	0.0467 (15)	0.079 (2)	0.0013 (11)	0.0099 (13)	0.0073 (15)
C1	0.0260 (17)	0.048 (2)	0.052 (3)	−0.0005 (15)	0.0026 (15)	−0.0044 (18)
C2	0.0262 (17)	0.049 (2)	0.045 (2)	0.0031 (15)	0.0001 (15)	0.0067 (18)
C3	0.037 (2)	0.063 (3)	0.055 (3)	0.0116 (19)	0.0094 (17)	0.002 (2)
C4	0.055 (3)	0.067 (3)	0.048 (2)	0.019 (2)	0.008 (2)	−0.004 (3)
C5	0.063 (3)	0.056 (3)	0.057 (3)	0.004 (2)	−0.003 (2)	−0.014 (2)
C6	0.0386 (19)	0.056 (2)	0.056 (3)	−0.0008 (17)	0.001 (2)	−0.003 (2)
C7	0.0298 (17)	0.0432 (19)	0.041 (2)	0.0063 (15)	0.0017 (14)	0.0017 (16)
C8	0.0181 (14)	0.0436 (19)	0.039 (2)	−0.0007 (13)	0.0007 (14)	0.0048 (15)
C9	0.0369 (19)	0.043 (2)	0.044 (2)	−0.0020 (15)	0.0103 (15)	−0.0058 (18)
C10	0.0317 (16)	0.0365 (17)	0.0409 (19)	−0.0003 (13)	0.0031 (16)	−0.0061 (18)
C11	0.040 (2)	0.0382 (19)	0.053 (2)	0.0127 (16)	−0.0037 (17)	0.0018 (18)
C12	0.053 (2)	0.044 (2)	0.058 (3)	0.0048 (18)	0.004 (2)	0.018 (2)
C13	0.0380 (19)	0.045 (2)	0.061 (2)	0.0019 (16)	0.012 (2)	0.008 (2)
C14	0.0308 (17)	0.0342 (18)	0.047 (2)	0.0037 (14)	−0.0004 (15)	−0.0007 (17)
C15	0.0311 (17)	0.0327 (17)	0.043 (2)	0.0026 (13)	0.0005 (14)	0.0016 (16)
C16	0.0291 (16)	0.0418 (19)	0.0431 (19)	0.0017 (14)	0.0027 (16)	−0.002 (2)

Geometric parameters (Å, º)

Cu1—N1	1.964 (3)	C3—C4	1.364 (7)
Cu1—O1	2.289 (3)	C3—H3	0.9300
Cu1—O2^i	1.938 (3)	C4—C5	1.391 (6)
Cu1—O4^ii	2.040 (3)	C4—H4	0.9300
Cu1—O5^ii	1.982 (3)	C5—C6	1.378 (7)
O1—C8	1.226 (4)	C5—H5	0.9300
O2—C8	1.267 (4)	C6—C7	1.383 (6)
O4—C16	1.255 (4)	C6—H6	0.9300
O5—C16	1.263 (4)	C8—C9	1.513 (5)
Cu1—C16^ii	2.344 (3)	C9—H9A	0.9700
N1—C1	1.305 (5)	C9—H9B	0.9700
N1—C7	1.401 (5)	C10—C11	1.388 (6)
N2—C1	1.336 (5)	C10—C15	1.377 (5)
N2—C2	1.377 (5)	C11—C12	1.373 (6)
N2—H17	0.8600	C11—H11	0.9300
O2—Cu1^iii	1.938 (3)	C12—C13	1.383 (6)
O3—C9	1.411 (5)	C12—H12	0.9300
O3—C10	1.367 (4)	C13—C14	1.380 (6)
O4—Cu1^iv	2.040 (3)	C13—H13	0.9300
O5—Cu1^iv	1.982 (3)	C14—C15	1.404 (5)
C1—H1	0.9300	C14—C16	1.478 (5)
C2—C3	1.382 (6)	C15—H15	0.9300
C2—C7	1.402 (5)	C16—Cu1^iv	2.344 (3)
N1—Cu1—O1	88.66 (13)	C2—C3—H3	121.5
N1—Cu1—O4^ii	165.18 (12)	C3—C2—C7	122.2 (4)
N1—Cu1—O5^ii	100.99 (12)	C3—C4—C5	121.2 (4)
O2^i—Cu1—N1	93.14 (12)	C3—C4—H4	119.4
O2^i—Cu1—O1	95.38 (11)	C4—C3—C2	117.0 (4)
O2^i—Cu1—O4^ii	101.58 (11)	C4—C3—H3	121.5
O2^i—Cu1—O5^ii	162.63 (12)	C4—C5—H5	118.8
O4^ii—Cu1—O1	88.25 (11)	C5—C4—H4	119.4
O5^ii—Cu1—O1	95.00 (12)	C5—C6—C7	116.7 (4)
O5^ii—Cu1—O4^ii	64.87 (11)	C5—C6—H6	121.7
N1—Cu1—C16^ii	133.28 (13)	C6—C5—C4	122.5 (4)
N1—C1—N2	113.1 (4)	C6—C5—H5	118.8
N1—C1—H1	123.4	C6—C7—N1	131.3 (4)
N2—C1—H1	123.4	C6—C7—C2	120.4 (4)
N2—C2—C3	132.5 (4)	C7—C6—H6	121.7
N2—C2—C7	105.3 (3)	C8—O1—Cu1	131.3 (2)
N1—C7—C2	108.3 (3)	C8—O2—Cu1^iii	117.9 (3)
O1—Cu1—C16^ii	90.74 (12)	C8—C9—H9A	108.9
O1—C8—O2	125.6 (4)	C8—C9—H9B	108.9
O1—C8—C9	117.2 (3)	C10—O3—C9	120.6 (3)
O2^i—Cu1—C16^ii	133.35 (12)	C10—C11—H11	119.8
O2—C8—C9	117.2 (3)	C10—C15—C14	119.4 (3)
O3—C9—C8	113.5 (3)	C10—C15—H15	120.3
O3—C9—H9A	108.9	C11—C12—C13	120.8 (4)
O3—C9—H9B	108.9	C11—C12—H12	119.6
O3—C10—C15	126.1 (4)	C12—C11—C10	120.5 (4)
O3—C10—C11	114.2 (3)	C12—C11—H11	119.8
O4^ii—Cu1—C16^ii	32.32 (11)	C12—C13—H13	120.6
O4—C16—Cu1^iv	60.39 (18)	C13—C12—H12	119.6
O4—C16—O5	118.0 (3)	C13—C14—C15	120.8 (3)
O4—C16—C14	121.1 (3)	C13—C14—C16	119.4 (3)
O5^ii—Cu1—C16^ii	32.59 (11)	C14—C13—C12	118.9 (4)
O5—C16—Cu1^iv	57.74 (18)	C14—C13—H13	120.6
O5—C16—C14	120.9 (3)	C14—C15—H15	120.3
C1—N1—C7	105.6 (3)	C14—C16—Cu1^iv	174.5 (3)
C1—N1—Cu1	125.1 (3)	C15—C10—C11	119.7 (3)
C7—N1—Cu1	128.3 (2)	C15—C14—C16	119.7 (3)
C1—N2—C2	107.8 (3)	C16—O4—Cu1^iv	87.3 (2)
C1—N2—H17	126.1	C16—O5—Cu1^iv	89.7 (2)
C2—N2—H17	126.1	H9A—C9—H9B	107.7
Cu1—N1—C1—N2	−169.6 (3)	C1—N1—C7—C6	179.2 (5)
Cu1—N1—C7—C2	169.2 (3)	C1—N2—C2—C3	179.6 (4)
Cu1—N1—C7—C6	−11.8 (6)	C1—N2—C2—C7	0.2 (5)
Cu1—O1—C8—O2	124.9 (3)	C2—N2—C1—N1	0.0 (5)
Cu1—O1—C8—C9	−57.5 (5)	C2—C3—C4—C5	0.5 (7)
Cu1^iii—O2—C8—O1	0.4 (5)	C3—C2—C7—N1	−179.8 (4)
Cu1^iii—O2—C8—C9	−177.2 (2)	C3—C2—C7—C6	1.1 (6)
Cu1^iv—O4—C16—O5	−3.5 (4)	C3—C4—C5—C6	0.2 (8)
Cu1^iv—O4—C16—C14	173.8 (4)	C4—C5—C6—C7	−0.3 (7)
Cu1^iv—O5—C16—O4	3.6 (4)	C5—C6—C7—N1	−179.3 (4)
Cu1^iv—O5—C16—C14	−173.7 (4)	C5—C6—C7—C2	−0.3 (6)
N1—Cu1—O1—C8	−45.8 (3)	C7—N1—C1—N2	−0.1 (5)
N2—C2—C3—C4	179.4 (5)	C7—C2—C3—C4	−1.1 (6)
N2—C2—C7—N1	−0.2 (4)	C9—O3—C10—C15	1.4 (6)
N2—C2—C7—C6	−179.4 (4)	C9—O3—C10—C11	−178.8 (3)
O1—Cu1—N1—C1	98.7 (4)	C10—O3—C9—C8	−85.0 (4)
O1—Cu1—N1—C7	−68.3 (3)	C10—C11—C12—C13	0.0 (7)
O1—C8—C9—O3	−157.2 (3)	C11—C10—C15—C14	1.7 (6)
O2^i—Cu1—N1—C1	3.4 (4)	C11—C12—C13—C14	0.6 (7)
O2^i—Cu1—N1—C7	−163.6 (3)	C12—C13—C14—C15	0.0 (7)
O2^i—Cu1—O1—C8	47.2 (3)	C12—C13—C14—C16	177.0 (4)
O2—C8—C9—O3	20.6 (5)	C13—C14—C15—C10	−1.1 (6)
O3—C10—C11—C12	179.0 (4)	C13—C14—C16—O4	−161.2 (4)
O3—C10—C15—C14	−178.5 (4)	C13—C14—C16—O5	16.1 (6)
O4^ii—Cu1—N1—C1	176.7 (4)	C15—C10—C11—C12	−1.1 (6)
O4^ii—Cu1—N1—C7	9.7 (8)	C15—C14—C16—O4	15.9 (6)
O4^ii—Cu1—O1—C8	148.7 (3)	C15—C14—C16—O5	−166.9 (4)
O5^ii—Cu1—N1—C1	−166.4 (3)	C16^ii—Cu1—N1—C1	−171.5 (3)
O5^ii—Cu1—N1—C7	26.5 (4)	C16^ii—Cu1—N1—C7	21.5 (4)
O5^ii—Cu1—O1—C8	−146.7 (3)	C16^ii—Cu1—O1—C8	−179.1 (4)
C1—N1—C7—C2	0.2 (4)	C16—C14—C15—C10	−178.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H17···O1^v	0.86	2.09	2.911 (4)	159
N2—H17···O4	0.86	2.64	3.088 (5)	114

Symmetry code: (v) x+1/4, −y+1/4, z+1/4.