Crystal structure of aqua­(1H-pyrazole-κN²)(pyridine-2,6-di­carboxyl­ato-κ³O²,N,O⁶)copper(II) dihydrate

The synthesis and crystal structure of tridentate pyridine-2,6-di­carboxyl­ate Cu^II complex with a heterocyclic pyrazole ligand, a potential candidate for metal catalysts, are reported. The Cu^II atom is coordinated by three O atoms and two N atoms, provided by a tridentate pyridine-2,6-di­carboxyl­ate, one pyrazole and one water ligand, forming a slightly distorted square-pyramidal geometry.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.088
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT354_ALERT_3_C Short  O-H (X0.82,N0.98A)  O19      - H19A     .       0.70 Ang.
PLAT354_ALERT_3_C Short  O-H (X0.82,N0.98A)  O20      - H20B     .       0.70 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.007 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          6 Report
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.96A   From O21             0.41 eA-3

Alert level G
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.22 Info
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         62 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Aqua(1H-pyrazole-κN²)(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)copper(II) dihydrate

Crystal data

[Cu(C7H3NO4)(C3H4N2)(H2O)]·2H2O	Z = 2
Mr = 350.77	F(000) = 358
Triclinic, P1	Dx = 1.705 Mg m^−3
a = 5.2171 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9249 (16) Å	Cell parameters from 9694 reflections
c = 15.309 (3) Å	θ = 2.4–28.2°
α = 105.289 (8)°	µ = 1.64 mm^−1
β = 94.523 (8)°	T = 296 K
γ = 93.295 (9)°	Block, green
V = 683.2 (2) Å^3	0.25 × 0.23 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3110 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −6→6
Tmin = 0.546, Tmax = 0.726	k = −11→11
15587 measured reflections	l = −20→20
3312 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0181P)^2 + 1.271P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max < 0.001
3312 reflections	Δρmax = 0.68 e Å^−3
214 parameters	Δρmin = −0.52 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
Cu1	0.72303 (6)	0.46457 (4)	0.26827 (2)	0.02692 (10)
N2	0.6036 (4)	0.3633 (2)	0.14415 (14)	0.0245 (4)
C3	0.7285 (5)	0.2455 (3)	0.09966 (17)	0.0262 (5)
C4	0.6564 (6)	0.1715 (3)	0.00900 (19)	0.0332 (6)
H4	0.7444	0.0895	−0.0224	0.040*
C5	0.4473 (6)	0.2238 (3)	−0.03373 (19)	0.0363 (6)
H5	0.3942	0.1762	−0.0947	0.044*
C6	0.3182 (6)	0.3459 (3)	0.01379 (19)	0.0328 (6)
H6	0.1778	0.3807	−0.0143	0.039*
C7	0.4036 (5)	0.4151 (3)	0.10435 (17)	0.0253 (5)
C8	0.9466 (5)	0.2086 (3)	0.16040 (18)	0.0288 (5)
O9	0.9876 (4)	0.3056 (2)	0.23975 (13)	0.0327 (4)
O10	1.0648 (5)	0.0935 (3)	0.13212 (15)	0.0443 (5)
C11	0.2971 (5)	0.5503 (3)	0.16952 (18)	0.0282 (5)
O12	0.4307 (4)	0.6002 (2)	0.24738 (13)	0.0319 (4)
O13	0.0961 (4)	0.6013 (3)	0.14620 (15)	0.0417 (5)
N14	0.8880 (4)	0.6023 (3)	0.38160 (16)	0.0330 (5)
N15	1.1120 (5)	0.6903 (3)	0.39067 (18)	0.0409 (6)
H15	1.218 (8)	0.680 (5)	0.344 (3)	0.066 (12)*
C16	1.1553 (7)	0.7888 (4)	0.4734 (2)	0.0530 (9)
H16	1.2963	0.8616	0.4944	0.064*
C17	0.9590 (8)	0.7642 (5)	0.5214 (2)	0.0583 (10)
H17	0.9378	0.8150	0.5814	0.070*
C18	0.7951 (7)	0.6469 (4)	0.4620 (2)	0.0492 (8)
H18	0.6417	0.6053	0.4765	0.059*
O19	0.4765 (5)	0.3250 (3)	0.33442 (17)	0.0397 (5)
H19A	0.356 (9)	0.304 (5)	0.309 (3)	0.061 (15)*
H19B	0.521 (8)	0.246 (5)	0.333 (3)	0.057 (14)*
O20	0.0431 (7)	0.9056 (3)	0.2509 (2)	0.0657 (8)
H20A	0.061 (10)	0.952 (6)	0.215 (4)	0.079*
H20B	0.042 (10)	0.828 (6)	0.226 (4)	0.079*
O21	0.5720 (7)	0.0147 (4)	0.3314 (3)	0.0839 (11)
H21A	0.420 (11)	−0.039 (7)	0.303 (4)	0.101*
H21B	0.676 (12)	−0.028 (7)	0.299 (4)	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02439 (16)	0.03062 (17)	0.02206 (16)	0.00556 (12)	−0.00065 (11)	0.00077 (12)
N2	0.0246 (10)	0.0259 (10)	0.0219 (10)	0.0018 (8)	0.0023 (8)	0.0047 (8)
C3	0.0272 (12)	0.0239 (11)	0.0268 (12)	0.0010 (9)	0.0047 (10)	0.0053 (9)
C4	0.0398 (15)	0.0276 (13)	0.0290 (13)	0.0014 (11)	0.0078 (11)	0.0011 (10)
C5	0.0445 (16)	0.0381 (15)	0.0217 (12)	−0.0033 (12)	−0.0001 (11)	0.0023 (11)
C6	0.0340 (14)	0.0364 (14)	0.0279 (13)	−0.0002 (11)	−0.0028 (11)	0.0107 (11)
C7	0.0239 (12)	0.0269 (12)	0.0253 (12)	0.0010 (9)	0.0025 (9)	0.0075 (9)
C8	0.0277 (13)	0.0292 (13)	0.0306 (13)	0.0043 (10)	0.0054 (10)	0.0089 (10)
O9	0.0276 (9)	0.0372 (10)	0.0306 (10)	0.0083 (8)	−0.0014 (7)	0.0042 (8)
O10	0.0511 (13)	0.0405 (12)	0.0425 (12)	0.0220 (10)	0.0085 (10)	0.0083 (9)
C11	0.0279 (13)	0.0290 (12)	0.0294 (13)	0.0057 (10)	0.0036 (10)	0.0097 (10)
O12	0.0311 (10)	0.0336 (10)	0.0277 (9)	0.0107 (8)	0.0012 (7)	0.0012 (8)
O13	0.0366 (11)	0.0424 (12)	0.0448 (12)	0.0166 (9)	−0.0044 (9)	0.0089 (9)
N14	0.0282 (11)	0.0387 (13)	0.0280 (11)	−0.0003 (9)	0.0003 (9)	0.0029 (10)
N15	0.0372 (14)	0.0487 (15)	0.0299 (13)	−0.0047 (11)	0.0072 (10)	−0.0011 (11)
C16	0.053 (2)	0.054 (2)	0.0371 (17)	−0.0137 (16)	0.0027 (15)	−0.0095 (15)
C17	0.059 (2)	0.072 (2)	0.0294 (16)	−0.0077 (19)	0.0098 (15)	−0.0112 (16)
C18	0.0427 (18)	0.068 (2)	0.0308 (15)	−0.0053 (16)	0.0080 (13)	0.0026 (15)
O19	0.0297 (12)	0.0496 (14)	0.0428 (13)	0.0017 (10)	0.0000 (10)	0.0188 (11)
O20	0.096 (2)	0.0400 (14)	0.0618 (19)	0.0135 (16)	0.0016 (16)	0.0158 (13)
O21	0.070 (2)	0.0589 (19)	0.106 (3)	0.0035 (16)	−0.021 (2)	0.0010 (18)

Geometric parameters (Å, º)

Cu1—N2	1.913 (2)	C11—O13	1.231 (3)
Cu1—N14	1.944 (2)	C11—O12	1.288 (3)
Cu1—O9	2.0255 (19)	N14—C18	1.329 (4)
Cu1—O12	2.0577 (19)	N14—N15	1.347 (3)
Cu1—O19	2.217 (2)	N15—C16	1.331 (4)
N2—C3	1.328 (3)	N15—H15	0.93 (4)
N2—C7	1.333 (3)	C16—C17	1.346 (5)
C3—C4	1.382 (4)	C16—H16	0.9300
C3—C8	1.519 (4)	C17—C18	1.388 (5)
C4—C5	1.394 (4)	C17—H17	0.9300
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.384 (4)	O19—H19A	0.70 (5)
C5—H5	0.9300	O19—H19B	0.75 (4)
C6—C7	1.386 (4)	O20—H20A	0.78 (5)
C6—H6	0.9300	O20—H20B	0.70 (5)
C7—C11	1.513 (4)	O21—H21A	0.91 (6)
C8—O10	1.226 (3)	O21—H21B	0.81 (6)
C8—O9	1.286 (3)
N2—Cu1—N14	166.22 (10)	O10—C8—O9	125.9 (3)
N2—Cu1—O9	80.44 (8)	O10—C8—C3	119.8 (2)
N14—Cu1—O9	100.39 (9)	O9—C8—C3	114.3 (2)
N2—Cu1—O12	79.55 (8)	C8—O9—Cu1	114.62 (16)
N14—Cu1—O12	97.91 (9)	O13—C11—O12	125.8 (2)
O9—Cu1—O12	159.43 (8)	O13—C11—C7	119.7 (2)
N2—Cu1—O19	98.60 (9)	O12—C11—C7	114.5 (2)
N14—Cu1—O19	95.05 (10)	C11—O12—Cu1	114.43 (16)
O9—Cu1—O19	94.79 (9)	C18—N14—N15	105.1 (2)
O12—Cu1—O19	92.87 (9)	C18—N14—Cu1	129.0 (2)
C3—N2—C7	122.1 (2)	N15—N14—Cu1	125.41 (19)
C3—N2—Cu1	118.43 (17)	C16—N15—N14	111.1 (3)
C7—N2—Cu1	119.42 (17)	C16—N15—H15	126 (3)
N2—C3—C4	121.0 (2)	N14—N15—H15	122 (3)
N2—C3—C8	111.8 (2)	N15—C16—C17	108.0 (3)
C4—C3—C8	127.3 (2)	N15—C16—H16	126.0
C3—C4—C5	117.7 (3)	C17—C16—H16	126.0
C3—C4—H4	121.1	C16—C17—C18	105.3 (3)
C5—C4—H4	121.1	C16—C17—H17	127.4
C6—C5—C4	120.6 (3)	C18—C17—H17	127.4
C6—C5—H5	119.7	N14—C18—C17	110.5 (3)
C4—C5—H5	119.7	N14—C18—H18	124.7
C5—C6—C7	118.3 (3)	C17—C18—H18	124.7
C5—C6—H6	120.9	Cu1—O19—H19A	110 (4)
C7—C6—H6	120.9	Cu1—O19—H19B	115 (3)
N2—C7—C6	120.3 (2)	H19A—O19—H19B	101 (5)
N2—C7—C11	111.7 (2)	H20A—O20—H20B	103 (6)
C6—C7—C11	128.0 (2)	H21A—O21—H21B	102 (5)
C7—N2—C3—C4	0.4 (4)	C4—C3—C8—O9	173.6 (3)
Cu1—N2—C3—C4	−177.8 (2)	O10—C8—O9—Cu1	−172.0 (2)
C7—N2—C3—C8	−179.6 (2)	C3—C8—O9—Cu1	7.5 (3)
Cu1—N2—C3—C8	2.3 (3)	N2—C7—C11—O13	−172.6 (2)
N2—C3—C4—C5	−0.5 (4)	C6—C7—C11—O13	7.5 (4)
C8—C3—C4—C5	179.4 (3)	N2—C7—C11—O12	6.4 (3)
C3—C4—C5—C6	0.1 (4)	C6—C7—C11—O12	−173.5 (3)
C4—C5—C6—C7	0.5 (4)	O13—C11—O12—Cu1	171.0 (2)
C3—N2—C7—C6	0.2 (4)	C7—C11—O12—Cu1	−7.9 (3)
Cu1—N2—C7—C6	178.3 (2)	C18—N14—N15—C16	−1.2 (4)
C3—N2—C7—C11	−179.7 (2)	Cu1—N14—N15—C16	170.8 (3)
Cu1—N2—C7—C11	−1.6 (3)	N14—N15—C16—C17	1.2 (5)
C5—C6—C7—N2	−0.6 (4)	N15—C16—C17—C18	−0.7 (5)
C5—C6—C7—C11	179.2 (3)	N15—N14—C18—C17	0.7 (4)
N2—C3—C8—O10	173.0 (3)	Cu1—N14—C18—C17	−170.9 (3)
C4—C3—C8—O10	−6.9 (4)	C16—C17—C18—N14	0.0 (5)
N2—C3—C8—O9	−6.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O19—H19B···O21	0.75 (4)	2.09 (5)	2.831 (5)	169 (4)
O20—H20B···O13	0.70 (5)	2.12 (5)	2.807 (4)	172 (6)
N15—H15···O12^i	0.93 (4)	1.93 (4)	2.832 (3)	164 (4)
O19—H19A···O9^ii	0.70 (5)	2.12 (5)	2.805 (3)	165 (5)
O20—H20A···O10^iii	0.78 (5)	2.01 (5)	2.784 (4)	171 (5)
O21—H21A···O20^iv	0.91 (6)	2.05 (6)	2.933 (5)	163 (5)
O21—H21B···O20^v	0.81 (6)	2.17 (6)	2.938 (5)	161 (6)

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