5-Carboxyl­ato-5-hydr­oxy-4-(4-methoxy­benzo­yl)-3-(4-methoxy­phen­yl)-1,1-dimethyl-4,5-dihydro-1H-pyrazol-1-ium monohydrate

In the title compound, C₂₁H₂₂N₂O₆·H₂O, the pyrazolium ring is in an envelope conformation. In the crystal structure, inter­molecular O—H...O hydrogen bonds form mol­ecular tapes along [001]. In addition, weak C—H...O and a C—H...π inter­action link mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.130
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.710
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.15
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............       0.71 e/A   3
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21B   ..  CG1     ..       3.01 Ang.

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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

5-carboxylato-5-hydroxy-4-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-1,1-dimethyl- 4,5-dihydro-1H-pyrazol-1-ium monohydrate

Crystal data

C21H22N2O6·H2O	F(000) = 880
Mr = 416.42	Dx = 1.331 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18802 reflections
a = 16.5325 (8) Å	θ = 1.8–28.0°
b = 16.0283 (11) Å	µ = 0.10 mm^−1
c = 7.8717 (4) Å	T = 296 K
β = 94.896 (4)°	Plate, colorless
V = 2078.3 (2) Å^3	0.49 × 0.37 × 0.18 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	2753 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 26.0°, θmin = 1.8°
Detector resolution: 6.67 pixels mm^-1	h = −20→20
rotation method scans	k = −19→19
19824 measured reflections	l = −9→9
4084 independent 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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0745P)^2 + 0.0106P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4084 reflections	Δρmax = 0.71 e Å^−3
280 parameters	Δρmin = −0.33 e Å^−3
16 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0073 (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
O1	0.36803 (8)	0.49197 (9)	0.44050 (17)	0.0423 (4)
H1	0.4081	0.4715	0.4023	0.063*
O2	0.48369 (9)	0.46283 (12)	0.6767 (2)	0.0614 (5)
O3	0.40206 (10)	0.39727 (10)	0.84515 (19)	0.0553 (4)
O4	0.15722 (9)	0.50954 (10)	0.4608 (2)	0.0526 (4)
O5	0.28545 (11)	0.87931 (9)	0.5119 (2)	0.0565 (4)
O6	−0.01103 (10)	0.36338 (12)	1.1485 (2)	0.0641 (5)
O7	0.47588 (14)	0.37338 (14)	0.1764 (2)	0.0737 (6)
H7A	0.460 (2)	0.384 (2)	0.063 (3)	0.120 (11)*
H7B	0.4879 (19)	0.4279 (13)	0.208 (4)	0.087 (9)*
N1	0.24977 (10)	0.33359 (11)	0.6103 (2)	0.0442 (4)
N2	0.31392 (10)	0.35724 (10)	0.5059 (2)	0.0403 (4)
C1	0.34661 (12)	0.44523 (12)	0.5734 (2)	0.0365 (4)
C2	0.27131 (12)	0.47772 (12)	0.6546 (2)	0.0361 (4)
H2	0.2883	0.5052	0.7630	0.043*
C3	0.22719 (12)	0.39837 (12)	0.6886 (3)	0.0387 (5)
C4	0.41855 (13)	0.43261 (13)	0.7131 (3)	0.0413 (5)
C5	0.37739 (14)	0.29067 (14)	0.5161 (3)	0.0509 (6)
H5A	0.4014	0.2864	0.6312	0.076*
H5B	0.4186	0.3045	0.4419	0.076*
H5C	0.3530	0.2383	0.4817	0.076*
C6	0.27759 (15)	0.36307 (15)	0.3241 (3)	0.0523 (6)
H6A	0.2367	0.4057	0.3154	0.079*
H6B	0.2536	0.3105	0.2900	0.079*
H6C	0.3194	0.3767	0.2512	0.079*
C7	0.21795 (12)	0.53750 (13)	0.5413 (3)	0.0395 (5)
C8	0.23922 (12)	0.62612 (13)	0.5367 (3)	0.0391 (5)
C9	0.18450 (13)	0.68183 (14)	0.4534 (3)	0.0463 (5)
H9	0.1361	0.6618	0.3996	0.056*
C10	0.20076 (14)	0.76572 (14)	0.4493 (3)	0.0514 (6)
H10	0.1628	0.8023	0.3968	0.062*
C11	0.27451 (13)	0.79592 (13)	0.5242 (3)	0.0441 (5)
C12	0.33036 (13)	0.74137 (14)	0.6039 (3)	0.0455 (5)
H12	0.3799	0.7612	0.6527	0.055*
C13	0.31248 (12)	0.65775 (13)	0.6108 (3)	0.0423 (5)
H13	0.3500	0.6215	0.6660	0.051*
C14	0.35977 (17)	0.91258 (16)	0.5908 (4)	0.0642 (7)
H14A	0.3608	0.9719	0.5739	0.096*
H14B	0.4048	0.8876	0.5407	0.096*
H14C	0.3635	0.9006	0.7107	0.096*
C15	0.16302 (12)	0.39318 (12)	0.8052 (3)	0.0404 (5)
C16	0.15889 (13)	0.44991 (14)	0.9369 (3)	0.0454 (5)
H16	0.1954	0.4941	0.9465	0.054*
C17	0.10169 (13)	0.44240 (15)	1.0545 (3)	0.0473 (5)
H17	0.1005	0.4806	1.1432	0.057*
C18	0.04648 (13)	0.37788 (15)	1.0391 (3)	0.0468 (5)
C19	0.04752 (15)	0.32217 (16)	0.9034 (3)	0.0573 (6)
H19	0.0087	0.2802	0.8898	0.069*
C20	0.10540 (14)	0.32905 (15)	0.7900 (3)	0.0527 (6)
H20	0.1065	0.2906	0.7017	0.063*
C21	−0.01000 (16)	0.4141 (2)	1.2977 (3)	0.0674 (7)
H21A	−0.0532	0.3973	1.3644	0.101*
H21B	−0.0172	0.4715	1.2651	0.101*
H21C	0.0411	0.4075	1.3640	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0439 (8)	0.0469 (8)	0.0375 (7)	0.0019 (6)	0.0119 (6)	0.0070 (6)
O2	0.0422 (9)	0.0837 (13)	0.0576 (10)	−0.0116 (8)	0.0014 (8)	0.0122 (9)
O3	0.0599 (10)	0.0630 (10)	0.0421 (9)	−0.0041 (8)	0.0001 (7)	0.0127 (7)
O4	0.0470 (9)	0.0484 (9)	0.0605 (10)	−0.0050 (7)	−0.0068 (8)	−0.0019 (7)
O5	0.0680 (10)	0.0369 (9)	0.0635 (10)	−0.0037 (7)	−0.0010 (8)	0.0029 (7)
O6	0.0536 (9)	0.0818 (12)	0.0601 (10)	−0.0179 (9)	0.0238 (8)	−0.0045 (9)
O7	0.0916 (15)	0.0770 (14)	0.0523 (11)	−0.0089 (11)	0.0043 (10)	0.0002 (10)
N1	0.0473 (10)	0.0415 (10)	0.0455 (10)	−0.0056 (8)	0.0143 (8)	−0.0030 (8)
N2	0.0466 (10)	0.0371 (9)	0.0383 (9)	−0.0010 (7)	0.0110 (8)	−0.0029 (7)
C1	0.0410 (10)	0.0350 (10)	0.0343 (10)	−0.0004 (8)	0.0080 (8)	0.0026 (8)
C2	0.0398 (10)	0.0345 (10)	0.0348 (10)	−0.0011 (8)	0.0071 (8)	−0.0015 (8)
C3	0.0422 (11)	0.0372 (11)	0.0368 (10)	−0.0015 (9)	0.0043 (8)	0.0002 (8)
C4	0.0439 (11)	0.0395 (11)	0.0407 (11)	0.0032 (9)	0.0051 (9)	0.0005 (9)
C5	0.0563 (13)	0.0415 (12)	0.0561 (14)	0.0079 (10)	0.0121 (11)	−0.0031 (10)
C6	0.0612 (14)	0.0562 (14)	0.0394 (12)	−0.0049 (11)	0.0026 (10)	−0.0093 (10)
C7	0.0402 (11)	0.0416 (11)	0.0379 (10)	−0.0003 (9)	0.0104 (9)	−0.0025 (9)
C8	0.0398 (10)	0.0385 (11)	0.0395 (10)	0.0007 (9)	0.0071 (9)	0.0015 (9)
C9	0.0404 (11)	0.0465 (12)	0.0515 (13)	−0.0003 (9)	0.0015 (10)	0.0049 (10)
C10	0.0478 (12)	0.0454 (13)	0.0602 (14)	0.0054 (10)	0.0002 (11)	0.0101 (10)
C11	0.0525 (12)	0.0353 (11)	0.0454 (12)	0.0010 (9)	0.0092 (10)	0.0024 (9)
C12	0.0460 (11)	0.0429 (12)	0.0470 (12)	−0.0035 (9)	0.0017 (10)	−0.0008 (9)
C13	0.0425 (11)	0.0394 (11)	0.0446 (11)	0.0033 (9)	0.0017 (9)	0.0016 (9)
C14	0.0824 (18)	0.0470 (14)	0.0615 (16)	−0.0152 (13)	−0.0026 (14)	−0.0044 (11)
C15	0.0420 (11)	0.0363 (11)	0.0436 (11)	−0.0025 (9)	0.0081 (9)	0.0027 (8)
C16	0.0461 (11)	0.0446 (12)	0.0465 (12)	−0.0097 (10)	0.0099 (10)	−0.0032 (10)
C17	0.0468 (12)	0.0549 (14)	0.0414 (11)	−0.0040 (10)	0.0102 (10)	−0.0053 (10)
C18	0.0398 (11)	0.0560 (13)	0.0457 (12)	−0.0018 (10)	0.0101 (9)	0.0051 (10)
C19	0.0514 (13)	0.0576 (15)	0.0645 (15)	−0.0190 (11)	0.0153 (12)	−0.0051 (12)
C20	0.0581 (14)	0.0493 (13)	0.0524 (13)	−0.0129 (11)	0.0152 (11)	−0.0098 (10)
C21	0.0591 (15)	0.091 (2)	0.0552 (15)	−0.0056 (14)	0.0246 (12)	−0.0037 (14)

Geometric parameters (Å, º)

O1—C1	1.358 (2)	C7—C8	1.464 (3)
O1—H1	0.8200	C8—C13	1.394 (3)
O2—C4	1.236 (3)	C8—C9	1.394 (3)
O3—C4	1.235 (3)	C9—C10	1.372 (3)
O4—C7	1.225 (2)	C9—H9	0.9300
O5—C11	1.353 (3)	C10—C11	1.395 (3)
O5—C14	1.432 (3)	C10—H10	0.9300
O6—C18	1.356 (3)	C11—C12	1.383 (3)
O6—C21	1.427 (3)	C12—C13	1.375 (3)
O7—H7A	0.925 (19)	C12—H12	0.9300
O7—H7B	0.927 (18)	C13—H13	0.9300
N1—C3	1.279 (3)	C14—H14A	0.9600
N1—N2	1.446 (2)	C14—H14B	0.9600
N2—C5	1.494 (3)	C14—H14C	0.9600
N2—C6	1.507 (3)	C15—C16	1.385 (3)
N2—C1	1.585 (3)	C15—C20	1.400 (3)
C1—C2	1.538 (3)	C16—C17	1.384 (3)
C1—C4	1.563 (3)	C16—H16	0.9300
C2—C3	1.501 (3)	C17—C18	1.378 (3)
C2—C7	1.536 (3)	C17—H17	0.9300
C2—H2	0.9800	C18—C19	1.394 (3)
C3—C15	1.463 (3)	C19—C20	1.367 (3)
C5—H5A	0.9600	C19—H19	0.9300
C5—H5B	0.9600	C20—H20	0.9300
C5—H5C	0.9600	C21—H21A	0.9600
C6—H6A	0.9600	C21—H21B	0.9600
C6—H6B	0.9600	C21—H21C	0.9600
C6—H6C	0.9600
C1—O1—H1	109.5	C9—C8—C7	119.03 (19)
C11—O5—C14	116.86 (19)	C10—C9—C8	121.2 (2)
C18—O6—C21	117.72 (19)	C10—C9—H9	119.4
H7A—O7—H7B	97 (3)	C8—C9—H9	119.4
C3—N1—N2	108.61 (16)	C9—C10—C11	119.7 (2)
N1—N2—C5	109.15 (16)	C9—C10—H10	120.1
N1—N2—C6	107.67 (16)	C11—C10—H10	120.1
C5—N2—C6	108.44 (16)	O5—C11—C12	124.7 (2)
N1—N2—C1	106.78 (14)	O5—C11—C10	115.45 (19)
C5—N2—C1	113.55 (16)	C12—C11—C10	119.9 (2)
C6—N2—C1	111.07 (15)	C13—C12—C11	119.8 (2)
O1—C1—C2	114.02 (16)	C13—C12—H12	120.1
O1—C1—C4	112.37 (16)	C11—C12—H12	120.1
C2—C1—C4	110.22 (16)	C12—C13—C8	121.3 (2)
O1—C1—N2	109.69 (15)	C12—C13—H13	119.3
C2—C1—N2	100.10 (14)	C8—C13—H13	119.3
C4—C1—N2	109.73 (15)	O5—C14—H14A	109.5
C3—C2—C7	111.63 (16)	O5—C14—H14B	109.5
C3—C2—C1	102.13 (15)	H14A—C14—H14B	109.5
C7—C2—C1	114.51 (15)	O5—C14—H14C	109.5
C3—C2—H2	109.4	H14A—C14—H14C	109.5
C7—C2—H2	109.4	H14B—C14—H14C	109.5
C1—C2—H2	109.4	C16—C15—C20	118.00 (19)
N1—C3—C15	120.87 (18)	C16—C15—C3	121.11 (18)
N1—C3—C2	115.80 (18)	C20—C15—C3	120.86 (19)
C15—C3—C2	123.32 (17)	C17—C16—C15	121.6 (2)
O3—C4—O2	129.3 (2)	C17—C16—H16	119.2
O3—C4—C1	116.27 (18)	C15—C16—H16	119.2
O2—C4—C1	114.35 (18)	C18—C17—C16	119.5 (2)
N2—C5—H5A	109.5	C18—C17—H17	120.3
N2—C5—H5B	109.5	C16—C17—H17	120.3
H5A—C5—H5B	109.5	O6—C18—C17	124.6 (2)
N2—C5—H5C	109.5	O6—C18—C19	115.6 (2)
H5A—C5—H5C	109.5	C17—C18—C19	119.8 (2)
H5B—C5—H5C	109.5	C20—C19—C18	120.3 (2)
N2—C6—H6A	109.5	C20—C19—H19	119.9
N2—C6—H6B	109.5	C18—C19—H19	119.9
H6A—C6—H6B	109.5	C19—C20—C15	120.8 (2)
N2—C6—H6C	109.5	C19—C20—H20	119.6
H6A—C6—H6C	109.5	C15—C20—H20	119.6
H6B—C6—H6C	109.5	O6—C21—H21A	109.5
O4—C7—C8	122.00 (19)	O6—C21—H21B	109.5
O4—C7—C2	118.48 (19)	H21A—C21—H21B	109.5
C8—C7—C2	119.50 (18)	O6—C21—H21C	109.5
C13—C8—C9	118.00 (19)	H21A—C21—H21C	109.5
C13—C8—C7	122.97 (19)	H21B—C21—H21C	109.5
C3—N1—N2—C5	139.58 (18)	C1—C2—C7—C8	−83.4 (2)
C3—N1—N2—C6	−102.90 (19)	O4—C7—C8—C13	−172.4 (2)
C3—N1—N2—C1	16.4 (2)	C2—C7—C8—C13	9.8 (3)
N1—N2—C1—O1	−144.83 (16)	O4—C7—C8—C9	7.0 (3)
C5—N2—C1—O1	94.82 (19)	C2—C7—C8—C9	−170.85 (19)
C6—N2—C1—O1	−27.7 (2)	C13—C8—C9—C10	−2.3 (3)
N1—N2—C1—C2	−24.64 (18)	C7—C8—C9—C10	178.3 (2)
C5—N2—C1—C2	−144.99 (16)	C8—C9—C10—C11	2.4 (4)
C6—N2—C1—C2	92.48 (17)	C14—O5—C11—C12	−1.3 (3)
N1—N2—C1—C4	91.27 (18)	C14—O5—C11—C10	178.7 (2)
C5—N2—C1—C4	−29.1 (2)	C9—C10—C11—O5	179.2 (2)
C6—N2—C1—C4	−151.61 (17)	C9—C10—C11—C12	−0.8 (3)
O1—C1—C2—C3	139.78 (17)	O5—C11—C12—C13	179.2 (2)
C4—C1—C2—C3	−92.76 (18)	C10—C11—C12—C13	−0.8 (3)
N2—C1—C2—C3	22.77 (17)	C11—C12—C13—C8	0.9 (3)
O1—C1—C2—C7	19.0 (2)	C9—C8—C13—C12	0.6 (3)
C4—C1—C2—C7	146.42 (17)	C7—C8—C13—C12	180.0 (2)
N2—C1—C2—C7	−98.05 (18)	N1—C3—C15—C16	154.5 (2)
N2—N1—C3—C15	−179.58 (17)	C2—C3—C15—C16	−24.6 (3)
N2—N1—C3—C2	−0.4 (2)	N1—C3—C15—C20	−23.5 (3)
C7—C2—C3—N1	106.9 (2)	C2—C3—C15—C20	157.5 (2)
C1—C2—C3—N1	−15.9 (2)	C20—C15—C16—C17	2.3 (3)
C7—C2—C3—C15	−74.0 (2)	C3—C15—C16—C17	−175.7 (2)
C1—C2—C3—C15	163.19 (18)	C15—C16—C17—C18	−1.1 (3)
O1—C1—C4—O3	173.61 (18)	C21—O6—C18—C17	−5.6 (3)
C2—C1—C4—O3	45.2 (2)	C21—O6—C18—C19	174.5 (2)
N2—C1—C4—O3	−64.1 (2)	C16—C17—C18—O6	178.6 (2)
O1—C1—C4—O2	−3.7 (3)	C16—C17—C18—C19	−1.6 (3)
C2—C1—C4—O2	−132.08 (19)	O6—C18—C19—C20	−177.1 (2)
N2—C1—C4—O2	118.6 (2)	C17—C18—C19—C20	3.0 (4)
C3—C2—C7—O4	−16.8 (3)	C18—C19—C20—C15	−1.8 (4)
C1—C2—C7—O4	98.6 (2)	C16—C15—C20—C19	−0.8 (4)
C3—C2—C7—C8	161.16 (17)	C3—C15—C20—C19	177.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O4	0.96	2.46	3.316 (3)	148
C5—H5A···O3	0.96	2.45	3.101 (3)	125
C16—H16···O5^i	0.93	2.54	3.465 (3)	172
O7—H7B···O2^ii	0.93 (2)	2.01 (2)	2.923 (3)	169 (3)
O7—H7A···O3^iii	0.93 (2)	1.90 (2)	2.809 (3)	167 (4)
C5—H5C···O3^iv	0.96	2.59	3.339 (3)	136
C21—H21C···O4^v	0.96	2.59	3.321 (3)	134
O1—H1···O2^ii	0.82	2.21	2.788 (2)	128
C14—H14C···O1^i	0.96	2.49	3.142 (3)	125
C21—H21B···Cg1^vi	0.96	3.01	3.9016	154

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